Reactive anthraquinone dyestuffs containing a fluoropyrimidinyl group

ABSTRACT

THE PRESENT INVENTION RELATES TO VALUABLE NEW REACTIVE DYESTUFFS OF THE GENERAL CONSTITUTION   4-R2,5-R1,F-,(D-N(-R)-)-PYRIMIDINE   IN THIS FORMULA D DENOTES THE RADICAL OF AN ORGANIC DYESTUFF, R IS HYDROGEN OR A LOWER ALKYL GROUP, R1 IS HYDROGEN OR SUBSTITUENT, R2 MEANS HYDROGEN, HALOGEN, OPTIONALLY SUBSTITUTED ALKYL, ALKENYL, ARALKYL OR ARYL RADICALS OR CARBOXYLIC ACID ESTER, CARBOXYLIC ACID AMIDE, ALKYL-SULPHONE AND ARYLSULPHONE GROUPS, AND F IS A FLUORO SUBSTITUENT.

United States Patent US. Cl. 260-256.5 R 19 Claims ABSTRACT OF THE DISCLOSURE The present invention relates to valuable new reactive dyestulfs of the general constitution in this formula D denotes the radical of an organic dyestulf, R is hydrogen or a lower alkyl group, R is hydrogen or a substitutent, R means hydrogen, halogen, optionally substituted alkyl, alkenyl, aralkyl or aryl radicals or carboxylic acid ester, carboxylic acid amide, alkyl-sulphone and arylsulphone groups, and F is a fluoro substituent.

This is a division of application Ser. No. 664,943 filed Sept. 1, 1967, now US. Patent 3,669,951.

In the dyestuifs of the general formula (-I) the group N(R) is linked directly to a carbon atom of the pyrimidine ring in the 2- or 4-position. On the other side the group N(R) is linked to an aromatic ring of the dyestuff D either directly or via a further bridge member, such as 40 or CO, as in the case of amide groupings, or via an alkylene group, an alkylene-CO--, an arylene, arylene-SO, arylene-CO or a triazine or diazine ring or an arylene-amidosulphonyl group. If such further bridge members contain heterocyclic ring systems, as is the case with triazinyl or pyrimidinyl radicals, these too, may contain reactive atoms or groupings, such as halogen atoms or other substituents of which large numbers are known.

Examples of substitutents R in the 5-position of the pyrimidine ring are: halogen, such as Cl, Br and F; alkyl radicals, such as CH and -C H substituted alkyl radicals, such as mono-, dior trichloroor tribromomethyl, trifluoromethyl radicals; alkenyl radicals, such as vinyl or halovinyl and allyl radicals; NO -CN, carboxylic acid, carboxylic acid ester and optionally N- substituted carboxylic acid or sulphonic acid amide groups, sulphonic acid and sulphonic acid ester groups, alkyl sulphonyl, aralkylsulphonyl or arylsulphonyl radicals.

Suitable substituents R in the 6-position of the pyrimidine ring are, for example, halogen, such as Cl, Br and F; alkyl, such as methyl and ethyl radicals; alkenyl, such as vinyl, halovinyl and allyl radicals; and substituted alkyl radicals, such as mono-, dior trichloroor bromo-methyl or trifluoromethyl radicals; carboxylic acid esters, such as the methyl and ethyl esters; carboxylic acid amide groups including the N-substitution products; alkylsulphonyl and arylsulphonyl radicals, such as CH3SO'2'', c2H5SOg-, and

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Dyestuffs in which R, and R denote hydrogen, halogen and/or alkyl radicals, belong to a preferred group of the compounds according to the invention.

The new dyestuffs may contain the radical once or several times in the molecule. Dyestuffs with 1 to 2 reactive radicals of this type are preferred for economic reasons.

Suitable pyrimidine rings 2-fluoro-4-pyrimidinyl, 2,6-difluoro-4-pyrimidinyl, 2,6difluoro-5-chloro-4-pyrimidinyl, 2-fiuoro-5,6-dichloro-4-pyrimidinyl, 2,6difluoro5-methyl-4-pyrimidinyl,

2,5 difluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl, Z-fluoro-S-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro4-pyrimidinyl, 2-fluoro-5cyano-4-pyrimidinyl, 2fluoro-5-methyl-4-pyrimidinyl, 2,5,6-trifluoro-4-pyrimidinyl, S-chloro-6-ch10romethyl-2fluoro-4-pyrimidinyl, 2,6difluoro-Sbromo-4-pyrimidinyl, 2-fluoro-5-bromo-6-methyl-4-pyrimidinyl, 2-fluoro-5-bromo-6-chloromethyl-4-pyrimidinyl, 2,6-difluoro-5chloromethyl-4-pyrimidinyl, 2,6-difluoro-Snitro-4-pyrimidinyl, 2-fluoro6-methyl-4-pyrimidinyl, Z-fiuoro-S-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-4-pyrimidinyl, Z-fluoro-6-chloro-4-pyrimidinyl, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl, 6trifluoromethyl-Z-fiuoro4-pyrimidinyl, 2*fluoro-5-nitro-4-pyrimidinyl, 2-fluoro-S-trifiuoromethyl-4-pyrimidinyl, Z-fluoro-S-methylsulphonyl-4-pyrimidinyl, Z-fluoro-Sphenyl-4-pyrimidinyl, Z-fluoro-S-carbonamido-4-pyrimidinyl, 2-fiuoro-S-carbomethoxy-4-pyrimidinyl, 2fluoro-S-bromo-6trifluoromethyl-4-pyrimidinyl, 2-fluoro-6-carbonamido-4-pyrimidinyl, 2-fiuoro-6-carbomethoxy-4-pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimidinyl, 2-fluoro-6-cyano4-pyrimidinyl, 2,6-difluoro-S-methylsulphonyl-4-pyrimidinyl, 2fluoro-5sulphonamido4-pyrimidinyl, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl, 2,6-difluoro-5-trifiuoromethyl4pyrimidinyl.

Among the many possibilities of attaching the radical (II) to D, the direct linkage of the groups N(R) to a carbon atom of a carbocyclic ring of D is preferred. Suitable bridge members of this or another kind, with the inclusion of the group N(R), are, for example (A standing for the radical of the formula III):

as well as the corresponding N-ethyland N-propylamides,

as well as the corresponding N-alkyl(15 C)-amides or -amines H, N I

/ Oorl in which B and E represent aromatic, carbocyclic or heterocyclic radicals and, in particular, B is the radical of a carbocyclic diazo component of the benzene or naphthalene series and E is the radical of an enolic or phenolic coupling component, e.g. a 5-pyrazolone, S-aminopyrazole, acetoacetic acid arylamide, hydroxynaphthalene or aminonaphthalene; B and B may otherwise contain any substituents customary in azo dyestuffs, including further azo groups; R stands for a CH group or, preferably for a hydrogen atom, and R' and R';, independently of one another, stand for hydrogen or halogen groups, such as Cl, Br or F.

Especially valuable dyestuffs of this series are those which are water-soluble and, in particular, those which contain sulphonic acid and/or carboxylic acid groups. The azo dyestuffs may be metal-free or metal-containing, the copper, chromium and cobalt complexes being the preferred metal complexes.

Important azo dyestuffs are, for example, those of the benzene-azo-naphthalene series, the benzene-azo-lphenyl-S-pyrazolone series, the benzene-azo-aminonaphthalene series, the naphthalene-azo-naphthalene-series, the naphthalene-azo-l-phenyl-pyrazolone-S series and the stilbene-azo-benzene series, the dyestuffs which contain sulphonic acid groups being again preferred. In the case of metal complex azo dyestuffs, the groups attached to the metal complex are preferably in the o-positions to the azo group, for example, in the form of 0,0'-dihydroxy-, ohydroxy-o'-carboxy-, 0-carboxy-o'-aminoand o-hydroxy-o'-aminoazo groupings. Particularly eminent types of monoazo dyestuffs of the kind obtainable according to the invention are illustrated by the following formulae:

NH; (or NET-alkyl) A-NH S 03H HO S 03H (lXa) HO NH-flWDo or 1 ll A-HN -N=N Os )1-a 3 30 to 1 (X) }(o) denotes that the stated radical stand in the adjacent (0) position to each other; A stands for the radical of the formula in which R' and R' have the same meaning as above;

or in other words, A stands for a 2-fluoropyrimidine-4- yl ring containing a radical R' in the -position and a radical R' in the fi-position, or A stands for a 4-fluoropyrimidine-Z-yl ring containing a radical R' in the 5- position and a radical R' in the 6-position; acyl stands for an acyl radical, in particular a lower aliphatic carbonyl or sulphonyl residue having 1 to 5 carbon atoms or an aryl carbonyl or aryl sulphonyl residue of the henzene and substituted benzene series; the nuclei drawn with dotted lines indicate that these nuclei may be present or absent.

2. Anthraquinone dyestuffs in which L and L denote substituents, especially sulphonic acid groups, p denotes an integer from 0 to 2, R" is a methyl or ethyl group or hydrogen, R' and R independently of one another, are hydrogen or halogen radicals. 3. Phthalocyanine dyestuffs (XII) groups, alkyl standing for alkyl radicals with l-3 carbon atoms.

The above compilation of a selection of suitable azo, anthraquinone and azaporphin dyestuffs and of fluorosubstituted pyrimidine rings does not represent a limitation of the general formulae, either with regard to the preparative possibilities of producing such dyestuffs within the scope of the general formula (I), or with regard to the valuable properties of these products in respect of application techniques. The new dyestuffs may otherwise contain any substituents customary in dyestuffs, such as sulphonic acid, carboxylic acid groups; sulphonamide and carbonamide groups which may be further substituted on the nitrogen atom of the amide; sulphonic acid ester and carboxylic acid ester groups; alkyl, aralkyl and aryl radicals; alkylamino, aralkylamino, arylamino, acylamino, nitro and cyano groups; halogen atoms such as Cl, Br and F; hydroxy, alkoxy, thioether, azo grouping and the like. The dyestuffs may also contain further groupings capable of fixation, such as monoor dihalo-triazinylamino, mono-, dior trihalo-pyrimidinylamino, 2,3-dihaloquinoxaline 6 carbonyl or -6 sulphonylamino, 1,4- dihalo-phthalazine-6-carbonylor -6-sulphonylamino, 2- haloor Z-alkylsulphonylor 2-arylsulphonyl-benzothiazole 5 carbonylor 5 sulphonylamino, alkylsulphonylpyrimidinyl, arylsulphonyl-pyrimidinyl, esterified sulphonic acid hydroxy alkylamide and hydroxy alkylsulphone groups, sulphofluoride-, haloalkylamino, acryloylamino, haloacylamino groups or other reactive groups.

The new dyestuffs of the formula (I) are obtained by introducing into dyestuffs or dyestulf intermediates, by known methods at least one fluoro-substituted pyrimidine ring linked via an amino group -N(R)-. If dyestutf intermediates are used, these are then converted into the desired final dyestuffs in known manner, particularly by a diazotising, and/or coupling and/or condensing reaction; in the formula (III) R denotes hydrogen or a substituent and R means hydrogen, halogen, optionally substituted alkyl, alkenyl, aralkyl or aryl radicals, carboxylic acid ester, carboxylic acid amide, alkylsulphone or an arylsulphone group; F stands for a fluorine atom.

The introduction into dyestuffs or dyestuff intermediates, of the radical (III) via an amino group -N(R)- can be carried out by various methods of preparation. For example, dyestuffs or dyestuff intermediates which contain amino or amide groups and exhibit a reactive hydrogen atom on the nitrogen atom of the amine or amide, can be reacted with compounds of the general formula R iI F R l N (XIII) in which R and R have the same meaning as above, F stands for a fluoro substituent and X for a radical which can be split off as an anion,

Heterocyclic pyrimidine compounds of the formula (XIII) which are suitable for the reaction are, for example:

2,4-difluoropyrimidine, 2,4-difiuoro-fi-methylpyrimidine, 2,6-difluoro-4-methyl-5-chloropyrimidine, 2,4,6-trifiuoropyrimidine, 2,4-difiuoropyrimidine-5-ethylsulphone, 2,6-difiuoro-4-chloropyrimidine, 2,4,5,6-tetrafluoropyrimidine, 2,4,6-trifiuoro-S-chloropyrimidine, 2,6-difluoro-4-methyl-5-bromopyrirnidine, 2,4-difiuoro-5,6-dichloroor -dibromopyrimidine, 4,6-difluoro-2,5-dichloroor -dibromopyrimidine, 2,6-difluoro-4-bromopyrimidine, 2,4,6-trifluoro-5-bromopyrimidine, 2,4,6-trifluoro-5-chloromethylpyrimidine, 2,4,6-trifiuoro-S-nitropyrimidine, 2,4,6-trifluoro-S-cyanopyrimidine, 2,4,6-trifluoropyrimidine-S-carboxylic acid alkyl esters or -5-carboxylic acid amides, 2,6-difluoro-5-methyl-4-chloropyrimidine, 2,6-difiuoro-5-chloropyrimidine, 2,4,6-trifiuoro-5-methylpyrimidine, 2,4,5-trifiuoro-6-methylpyrimidine, 2,4-difluoro-5-nitro-6-chloropyrimidine, 2,4-difluoro-S-cyanopyrimidine, 2,4difiuoro-S-methylpyrimidine, 6-trifluoromethyl-5-chloro-2,4-difluoro-pyrimidine, 6-phenyl-2,4-difiuoropyrimidine, 6-trifluoromethyl-2,4-difluoropyrimidine, 5-trifiuoromethyl-2,4,6-trifluoropyrimidine, 5-trifluoromethyl-2,4-difluoropyrimidine, 2,4-difluoro-S-nitropyrimidine, 2,4-difluoro-5-trifluoromethylpyrimidine, 2,4-difluoro-5-methylsulphonyl-pyrimidine, 2,4difluoro-S- henylpyrimidine, 2,4-difiuoro-5-carbonamido-pyrimidine, 2,4-difluoro-S-carbomethoxy-pyrimidine, 2,4-difluoro-G-trifluoromethylpyrimidine, 2,4-difluoro-5-bromo-6-trifiuoromethyl-pyrimidine, 2,4-difluoro-6-carbonamido-pyrimidine, 2,4-difluoro-6-carbomethoxy-pyrimidine, 2,4-difluoro-6-phenylpyrimidine, 2,4-difiuoro-6-cyanopyrim'idine, 2,4,6-trifluoro-S-methylsulphonyl-pyrimidine, 2,4-difiuoro-5-chloro 6-carbomethoxy-pyrimidine, 2,4-difluoro-S-sulphonamido-pyrimidine.

In the condensation reaction with the dyestuffs or dyestulf intermediates containing amino or amide groups, these pyrimidine derivatives can be assumed to react in the 4-position, the radical X being split off. In the general formulae (I), (II) and (IV) to (XII) the pyrimidine ring is therefore presumably and preferably attached via the 4-position to the radical of the dyestuff containing the N(R)- or N(R')-group.

The fluoro-pyrimidine compounds mentioned above and others which can be used according to the invention are generally readily obtained by reacting the corresponding chloro or bromo compounds with alkali metal fluorides, for example, with potassium fluoride, NaHF KSO F, SOF AgF or by reacting corresponding OH compounds with SF COF COClF or cyanuric fluoride, or by heating corresponding diazonium tetrafluoroborates.

Particularly preferred for the reaction according to the invention are those reactive components which correspond to the formula in which R and R' independently of one another, denote hydrogen or halogen radicals (Cl, Br or F), and Y is a radical which can be split off as an anion, particularly a fluoro substituent.

The reaction of the dyestuffs or dyestuff intermediates containing amino or amide groups with heterocyclic compounds of the formula (XIII) is carried out in accordance with the type of starting compounds used in an organic, aqueous-organic or aqueous medium at temperatures of 10 C. to 0., preferably at 0 to 50 C., in the presence of alkaline condensation agents, such as aqueous alkali metal carbonate or alkali metal hydroxide solutions.

If dyestuff intermediates are used, the condensation products obtained are converted in usual manner into the desired final dyestuffs. This process is primarily interesting for the preparation of azo dyestuffs in that, for example, a diazo and/ or coupling component containing a reactive amino or amido group, is first reacted with the reactive component (XIII) or (XIV) and the resultant intermediate subsequently converted by diazotisation and/or coupling and/ or condensation into an azo dyestulf. In the latter further conversion reactions as are customary in azo dyestuffs can subsequently be carried out, for example, acrylating, condensing, reducing and metallising reactions.

Also when preparing other dyestuffs, especially those of the phthalocyanine and anthraquinone series, the condensation of a reactive component (XIII) or (XIV) can first be performed with an intermediate, for example, with m-phenylene diamine or an m-phenylene diamine sulphonic acid, and the reaction product obtained can subsequently be further condensed with anthraquinone-sulphonic acid halide or with a copperor nickel-phthalocyanine-sulphonic acid halide to form a reactive phthalocyanine dyestuff.

Another variant for the preparation of the new dyestuffs of the formula (I) which is applicable in some cases consists in that in dyestuffs or, in particular, in dyestuff intermediates which contain at least one group of the general formula in which R, R and R have the same meaning as above and Z represents a radical which can be split off as anion, with the exception of a fiuoro substituent,

Z is exchanged in known manner for a fluoro substituent and, if dyestuff intermediates are used, these are subsequently converted into the desired final dyestuffs. The exchange of one or more substituents Z which can be split off as anions, for example, of Clor Br-atoms, for fluoro substituents can be carried out, for example, in the manner already explained.

As has already been mentioned for some cases, the dyestuffs obtainable by the various methods described above can be subjected to further reactions which are customary for deystuffs in that, for example, metallisable dyestuffs are treated with metal-yielding agents, especially with chromium, cobalt, copper or nickel salts; dyestuffs containing reducible groups, especially nitro groups, are reduced; dyestuffs containing acrylatable groups, especially acrylatable amino groups, are acylated; or dyestuffs are subsequently treated with sulphonating agents, such as chlorosulphonic acid, oleum or S0 in chlorinated hydrocarbons, in order to introduce (further) sulphonic acid groups into the products. The last mentioned process is sometimes of particular importance in the series of anthraquinone and phthalocyanine dyestuffs. Dyestuffs of the formula (I) which contain sulphonic acid and/or carboxylic acid groups are preferred within the scope of the present invention.

Depending upon the number of reactive-HNR-groupings suitable for the conversion reaction which are present in the dyestufr radical or dyestuif intermediates, one or more groupings of the general formula (II) can be incorporated with the dyestuffs. In the majority of cases the number m =4 will not be exceeded, but it is also possible to synthetise dyestuffs, especially those of a higher molecular structure, with more than 4, eg with up to 8 groupings of the formula (II).

If the dyestuffs produced according to process contain groups forming metal complexes, these can be converted into their metal complex compounds by the action of metal-yielding agents, for example, of copper, nickel, chromium or cobalt salts. They can also be subjected to other conventional conversion reactions, such as diazotizing, coupling acylating and condensing reactions.

The reaction of dyestuffs containing amino groups with reactive components of the formula (XIII) or (XIV) yields groups of particularly preferred dyestuffs, if those amino group-containing starting dyestuffs are used, from which the dyestuffs of the formulae (IV) to (XII) are derived, i.e. those containing the grouping N(R)H or --N(R")-H, instead of the group I A .1I l N F L NJ or the group -N(R')A.

In the production of phthalocyanine dyestuffs it is possible to prepare first a diaminoaryl compound which is mono-condensed with the reaction component (XIII) or (XIV) and subsequently to condense this with, preferably, copperor nickel-phthalocyanine-su1phonic acid halides; other amino compounds, such as ammonia, aliphatic amino compounds and/or aromatic amino compounds may be added simultaneously or subsequently. In this way, there are obtained phthalocyanine-, preferably cop peror nickel phthalocyanine sulphonamide dyestuffs which contain a certain proportion of sulphonarylamide groups carrying the reactive group and, in addition, a certain proportion of non-reactive sulphonamide groups and/or free sulphonic acid groups. Likewise, copperor nickel-phthalocyanine-sulphonic acid-(aminoaryl)-amides which may contain additional, optionally N-substituted sulphonamide groups of different type and free sulphonic acid groups, can be condensed on the amino group of the aminoaryl radical with reactive components (XIII) or (XIV) to form the new dyestuffs (I).

The new dyestuffs are extremely valuable products which are suitable for a great variety of applications. As water-soluble compounds they are primarily of interest for the dyeing of textile materials containing hydroxyl groups and containing nitrogen, especially textile materials of natural and regenerated cellulose, and also of wool, silk, synthetic polyamide and polyurethane fibres. Due to the reactive fluoro substituent or substituents in the pyrimidine ring, the products are particularly well suited as reactive dyestuffs for the dyeing of cellulose materials by the methods which have recently become known for this purpose. The fastness properties obtained, especially the fastness to wet processing, are excellent.

For dyeing cellulose, the dyestuffs are preferably used in an aqueous solution to which compounds of alkaline reaction, such as alkali metal hydroxide or alkali metal carbonate, or compounds which can be converted into substances of alkaline reaction, such as alkali metal bicarbonate, Cl C--OOO'Na, can be added. Further auxiliaries may be added to the solution, but these should not react with the dyestuffs in an undesirable manner. Additives of this kind are, for example, surface-active substances, such as alkylsulphates; substances preventing the migration of the dyestuif; dyeing auxiliaries such as urea; or inert thickening agents, such as oil-in-water emulsions, tragacanth, starch, alginate or methyl cellulose.

The solutions or pastes thus prepared are applied to the material to be dyed, for example, by padding on a I0 foulard (short bath) or by printing, followed by heating for some time at an elevated temperature, preferably 40 to 150 C. Heating can be carried out in a hot flue, in a steaming apparatus, on heated rollers or by introducing the material into heated concentrated salt baths, alone or successively in any sequence.

If a padding liquor or dyebath without alkali is used, the dry material is subsequently passed through a solution of alkaline reaction to which common salt or Glaubers salt has been added. The addition of salt prevents the dyestuff from migrating from the fibre.

The material to be dyed can also be previously treated with one of the acid-binding agents mentioned above, subsequently treated with the solution or paste of the dyestuff and finally fixed at an elevated temperature as stated.

For dyeing from a long bath, the material is introduced into an aqueous solution of the dyestuif (liquor ratio 1:5 to 1:40) at room temperature and dyeing is carried out for 40 to minutes, possibly with an increase of temperature up to 2090 C., preferably 30* 50 C., while adding portions of salt, for example, sodium sulphate, and subsequently of alkali, for example, sodium phosphates, sodium carbonate, NaOI-I or KOH. The chemical reaction between the dyestuff and the fibres takes place during this operation. After chemical fixation, the dyed material is rinsed hot and finally soaped, whereby unfixed residues of the dyestuff are removed. Dyeings of excellent fastness, especially fastness to wet processing and light, are obtained.

In the so-called cold batch padding process, the subsequent heating of the padded fabric can be saved by storing the fabric at room temperature for some time, for example 2 to 20 hours. In this process there is used a stronger alkali than in the dyeing process from a long bath described above.

For printing materials containing hydroxyl groups, there is used a printing paste consisting of the dyestuff solution, a thickening agent, such as sodium alginate, and a compound of alkaline reaction or splitting off alkali upon heating, such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate or sodium or potassium hydrogen carbonate, and the printed material is rinsed and soaped.

If the dyestuffs contain groupings forming metal complexes, the fastness properties of the dyeings and prints can frequently be improved by an after-treatment with metal-yielding agents, such as copper salts, for example, copper sulphate, chromium, cobalt or nickel salts, such as chromium acetate, cobalt sulphate or nickel sulphate.

Textile materials containing amide groups, such as wool, silk, synthetic polyamide and polyurethane fibres, are generally dyed by the dyeing methods customarily used for this purpose in the acid to neutral range, a final increase of the pH value of the dye bath, for example, to pH 6.5 to pH 8.5, being sometimes of advantage.

For example, the dyestuffs are applied to synthetic polyamide fabrics as solutions or, preferably, in dispersed form and subsequently after-treated, optionally together with (preferably smaller amounts) of acid-binding agents, such as sodium carbonate. Particularly advantageous re sults are achieved with those dyestuffs which are insoluble or only sparingly soluble in water. These are worked up by usual methods and with the addition of the known auxiliaries to form a dyestuff dispersion and are applied in this form in the dye bath and/ or padding liquor or in a printing paste. Auxiliaries suitable for this application are, inter alia, compounds which prevent the migration of the dyestuff on the fibre, such as cellulose ethers, alkali metal chlorides and sulphates; wetting agents, such as condensation products from ethylene oxide and fatty alcohols or phenols, sulphonated fatt alcohols; solvents, such as thiodiglycol; and also thickening agents, such as starch, tragacanth, alginate thickening, gum arabic etc.

The after-treatment of the dyeings, impregnations and prints obtained on fabrics of polyamide fibres is preferably carried out at a temperature of 50 to 110 C. for to 60 minutes. In the case where the dyestuffs used contain groupings forming metal complexes, the fastness properties of the dyeings can again sometimes be improved with metal-yielding agents, such as copper salts, for example, copper sulphate, or chromium, cobalt and nickel salts, such as chromium acetate, cobalt sulphate or nickel sulphate.

The dyeings which can be obtained with the new dyestuffs are generally characterised by good to very good fastness properties, especially by excellent fastness to wet processing.

Compared with the constitutionally most closely related known reactive dyestuffs containing chloroor bromopyrimidinylamino groups, as are described, for example, in Belgian Patent Specifications Nos. 572,973; 573,299 and 578,742, the new products of the formula (I) have essential advantages with regard to application techniques. In comparison with the cost closely related trichloropyrimidinyl dyestuffs, for example, the new dyestuffs which contain a 2,6 difluoro-S-chloro-pyrimidinylamino radical, surprisingly, give a better dyestuff yield on cotton and regenerated fibres and are superior with regard to colour depth when dyed from a long bath. In contrast to the known chloropyrimidine reactive dyestuffs, the new fluoropyrimidine reactive dyestuffs are also well suited for the so-called cold batch padding process for cotton and regenerated fibers. In the printing precess the new dyestuffs can be used for rapid fixation. The bond between the fibre and the dyestuffs in an alkaline medium is frequently stronger than with the known dyestuffs.

The new fluoropyrimidine reactive dyestuffs are also superior to the known chloropyrimidine dyestuffs in that they yield valuable dyeings of good fastness to washing, milling and potting on wool. Dyeings which are fast to wet processing can also be obtained on silk and synthetic superpolyamide and -polyurethane fibres.

In the following Examples the parts are parts by weight, unless otherwise stated.

EXAMPLE 1 To a solution of 34.7 parts of the sodium salt of 2- aminonaphthalene 4,8 disulphonic acid and 7 parts sodium nitrite in 300 parts of water there are added 28 parts by volume of concentrated hydrochloric acid, while cooling with ice, and the mixture is stirred at 010 C. for /2 hour. After removing the excess nitrous acid, 10.7 parts 3-amino-toluene dissolved in parts of concentrated hydrochloric acid and 150 parts of water are added and the coupling is completed by neutralising the mixture to pH 3-5. The resultant aminoazo dyestuft is salted out, filtered off with suction, washed and then redissolved at pH 7 to 140 parts of water and 200 parts acetone with the addition of a sodium hydroxide solution. 192 parts 2,4,6 trifluoro 5 -chloro pyrimidine are added dropwise to this solution at 2030 C. and a pH of 5.5-6 is maintained by means of a 2N sodium carbonate solution. When the reaction is completed, the resultant dyestufi of the presumable formula is salted out with 210 parts of a saturated sodium chloride solution, the product which crystallises in the form of yellow needles is filtered off with suction, washed with a 2% sodium chloride solution and dried in a vacuum at 50 C.

When a cellulose fabric is printed with a printing paste which contains, per kilogram, g. of the dyestulf, 100 g. urea, 300 ml. of water, 500 g. of alginate thickening (60 g. sodium alginate per kg. of thickening) and 20 g. sodium carbonate, and which has been made up with water to 1 kilogram, the fabric is then dried, steamed at C. for 1 minute, rinsed with hot water and soaped at the boil, an intense reddish yellow print of good fastness to washing and light is obtained.

EXAMPLE 2 0.1 mole of the copper complex compound of the formula (prepared according to the instructions of German Patent Specification No. 1,117,235 by coupling diazotised 1- amino 8 (benzene sulphonyloxy) naphthalene disulphonic acid-(3,6) in a soda-alkaline medium with the equivalent amount of Z-acetylamino 5 hydroxynaphthalene-disulphonic acid-(4,8), conversion of the monoazo compound into the copper complex by oxidative coppering, and hydrolysis of the acetyl and benzene-sulphonyl groups) are dissolved at pH 66.5 in 2500 parts by volume of water at 60-65 C. and mixed at 20-30 C. with 0.12 mole 2,4,6-trifluoro-5-chloropyrimidine.

A pH of 6-6.5 is maintained during the condensation by the addition of a sodium carbonate solution. When the reaction is completed, the dyestuff is salted out and isolated. When dried, the dyestuff is a dark powder which dissolves in water to give a a blue colour.

100 parts by weight of a cotton fabric are treated on the foulard at room temperature with an aqueous solution containing 2% of the dyestuff, 15 g. litre of sodium hydrogen carbonate and 150 g./litre of urea, subjected to intermediate drying, heated at C. for 2 minutes, then rinsed and soaped at the boil. The fabric is dyed in very clear blue shades fast to wet processing.

EXAMPLE 3 46 parts of the monoazo dyestuff obtained in analogy with Example 1 by coupling diazotised Z-aminonaphthalene-4,8-disulphonic acid with 3-methylamino-toluene are dissolved at 20-30 C. in 400 parts of water and 100 parts acetone, and 20 parts 2,4,6-trifluoro-5-chloropyrimidine are added dropwise while maintaining a pH of 6-7 by means of a 2N sodium carbonate solution; the condensation is continued until a sample no longer exhibits a change of colour when acidified. The resultant dyestuff which has the presumable formula H O as F I J N l CH3 1 F is salted out, filtered ofI with suction, washed and dried at 30 C. in a vacuum.

A cotton fabric is impregnated with a solution at 20- 25 C., which contains, per litre of liquor, 20 g. of the above dyestuif and 0.5 g. of non-ionic Wetting agent (e.g. a polyhydroxyethylated oleyl alcohol) as well as g. urea and 15 g. sodium bicarbonate. The fabric is subsequently squeezed between two rubber rollers to a moisture content of about 100%. After an intermediate drying at 50-60 C., the fabric is heated at 140 C. for 2 minutes, the dyeing so obtained is thoroughly rinsed with hot water and treated at the boil for 20 minutes with a solution containing, per litre, 5 g. of Marseilles soap and 2 g. sodium carbonate. After rinsing and drying, there is obtained an 13 intense reddish yellow dyeing of good fastness to wet processing, rubbing and light.

In the following Table there are listed the diazo components, coupling components and reactive components linkable to the amino group, from which dyestuffs can be synthetised in analogy with the instructions given in Examples l -3, the shades-obtained by one of the methods of application described above-being likewise stated in the Table.

Abbreviations for the reactive components:

Reactive Ex. Coupling com- No. Diazo component component ponent Shade 4-.." Z-aminonaphtlial-amino-Z-methoxy- A Yellow.

1ene-4,8-disu1- fi-methylbeuzene. phonic acid. do r do B Do. 6...-. I-aminonaphtha- 1-amino-3-methyl- A Do.

lene-3,6-disulbenzene. phonic acid. 7.. do Y do B Do. 8..... 2-aminonaphtha- .....do A Do.

lene-ii,7-disulphonic acid. 9. do do B Do; 10.... 2-aminonaphthado A Do.

lene-6,8-disul phonic acid. 11- do do 13 D0. 12-... 4-aminoazobenzenedo A Brown- 3,4-disulphonic yellow; acid. 13.... 1-aminobenzene4- do B Do.

sulphonic acid l-aminonaphthalene-fi-sulphonic acid. 14...- 2-(3-su1pho-4- do. A Yellow.

aminophenyl)-6- methylbenzothiazole-7-sulphonie acid. 15..-. 2-aminonaphtha- I-methylamino-B- B De.

lone-4,8-disulmethoxybenzene. phonic acid. 16....'.....do 1-amino-3-acetyl- A Do.

aminobenzene. Aniline A Do;

EXAMPLE 18 To a solution of 36.5 parts of the sodium salt of lamino-8hydroxynaphthalene-3,6-disulphonic acid in 200 parts of water there are added dropwise at 8-10 C. 20 parts 2,4,6-trifiuoro5-chloropyrimidine, and a pH of 5.5- 6 is maintained by continuous neutralisation of the liberated hydrogen fluoride. The reaction is observed by chromatography. The resultant solution of the dyestuff intermediate is poured into 900 parts of water and coupled at a pH of 7-8 and at 0-5 C. with 17.5 parts of diazotised 2- aminobenzene-sulphonic acid dissolved in 200 parts of Water. The product is salted out at a final pH of 6.5 with 80 parts sodium chloride, filtered oif with suction and washed with a 10% sodium chloride solution. Drying is carried out in a vacuum at 30-40 C. The dyestutr' N I scan on NH \I forms red small needles.

When a fabric of cotton or regenerated cellulose is dyed or printed with this dyestuff according to one of the processes described in Examples 1-3, clear bluish red dyeings and prints of good fastness to wet processing, rubbing and light are obtained.

Equally good results are obtained by the following method:

50 g. of a cotton skein are dyed in 1 litre of a dyebath containing 1.5 g. of the above dyestuflf by adding 50 g. sodium chloride in several portions at 20 to 30 C. within 30 minutes, subsequently adding 20 g. sodium carbonate and treating the material at the same temperature for 60 minutes. After rinsing, soaping at the boil and drying, a bluish red dyeing of good fastness to wet processing, rubbin g and light is obtained.

In the following Table there are listed the shades of further dyestuffs which are synthetised from the likewise specified diazo components, coupling components and reactive components linkable to the amino group in the latter, in analogy with the instructions given in Example 18 or also by reacting the corresponding aminoazo dyestuif with the reactive components, and which can be dyed or printed on to cellulose materials by one of the methods described above:

Abbreviations for reactive components as in Table of Example 3.

Reactive Ex. Coupling com- N o. Diazo component component ponent Shade 19...- 1-aminobcnzene-2- l-amino-S-hydroxy- B Red.

sulphonic acid. naphthalene iifidisulphonic acid.

20.-.. Aminobenzene 1-(3-aminobenzene- A Red.

amino)-8-hydroxynaphthalene-3,6- disulphonic acid.

21. do do B Red.

22--.. l-amino-Zcarboxyl-amino-S-hydroxy- A Red.

benzene-4-sulnaphthalene-3,6- phonic acid. disulphonic acid.

23.-.- l-aminot-methyl- ...-.do A Red.

benzene-2-sulphonic acid.

24.-.- 1-amino-3'acetyl- :.--.do B Red.

aminobenzene-B- sulphonic acid.

25.... 1-amino-3-(2-[4- -.....do A Red.

26-... l-aminobenzene- Z-amino-B-hydroxy- A Orange.

sulphonic acid. naphthalene-7- sulphonic acid.

269.... 1-arnino3-(2-[4- 2-amino-5-hydroxy- A Do.

sulphophenylnaphthalene-7- amino]-4-mcthy1- sulphonic acid. amin0triazine-1',- 3,5'-y1-6)- aminobenzene-G- sulphonic acid. 27.-.. l-aminobenzene- 2-methylamino-5- A Do.

2-sulphonic acid. hydroxy-naththalene-7-sulphonic acid. 28-... l-amino-acetyldo A Scarlet;

amino-G-sulphonic acid.

29 ..do Z-amino-S-hydroxy- A Do.

naphthalene-7- sulphonic acid.

EXAMPLE 30 To a solution of 21 parts of the sodium salt of 1,3- diaminobenzene-G-sulphonic acid in parts of Water there are added with good stirring 20.0 parts 2,4,6-trifiuoro-S-chloropyrimidine and the mixture is stirred at 20-30 C., while continuously neutralising the liberated hydrofluoric acid to pH -6-7, until a sample which is diazotised and coupled with l-hydroxynaphthalene-4- sulphonic acid yields a clear yellowish red coloration. The resultant dyestuif intermediate is directly diazotised, after the addition of ice, with 7 parts sodium nitrite and 28 parts of concentrated hydrochloric acid and subsequently combined with a previously prepared solution of 47 parts of the sodium salt of l-benzoylamino-8-hydroxynaphthalene-3,6-disulphonic acid and 12 parts sodium carbonate in 200 parts of Water, whereby coupling takes place to give the dyestuif of the formula ably acylatable amino group, from a coupling component and from a reactive component linkable with the diazo component. The methods described above can be used for dyeing and printing cellulose materials with the dyestuffs of the Table.

Abbreviations for reactive components as in Table of 16 with a copper-yielding agent, are dissolved at pH 7 in 1500 parts of Water. 20.0 parts of 2,4,6-trifluoro-5-chloropyrimidine are added dropwise at 2030 C. with good stirring, and the liberated hydrofluoric acid is continuously neutralised to a pH of 6-7 by means of a sodium carbonate solution. When free amino groups can no longer be detected, the resultant reactive dycstuif of the formula Example 3 1s salted out, pressed off, washed and dried in a vacuum Reactive pH of Example corncoupling number Diazo component Coupling component ponent medium Shade 31 1,3-diamlnobenzene-4- 2-aminonaphthalene-5,7-disulphonicacid A 4-6 Orange.

sulphonic acid. 32 ..do 2-aminonaphthalene-3,6-d.isulphonic acid A 4-5 Do. 2-aminonaphthalene-6-sulphonic acid B 4 5 Do. 2-N-methylamino-8-hydroxynaphthalene-fi-s 1p A 4-5 Do 35 -.do 1-(3,5'-Ciehloro-l,2'-thiazole-4-carbonamido)-8-hydroxy- A 7-8 Red naphthalene-3,6-disulphonic acid. 36 ..do l-(2, -dihydroxytriazine-1,3,5'-yl-6'-amino)-8-hydroxy- B 7-8 Red naphthalene-3,6-disulphonic acid. 1-(3,5-dichloro-1,2-thiaz0le-4-carbonamido)-8-hydr0xy- A 7-8 Red naphthalene-3,fi-disulphonic acid. 2-hydroxynaphthalene-3,fi-disulphonicacid A 8 Scarlet 1-acetylamin0-8-hydroxynaphthalene-3,6-disulphonic ae1d... B 7-8 Red. 1-(3-su1phophenyl)-3-methyl-pyrazolone-5 A 6 Yellow 1-(2,5-dich1oro-4-sulphophenyl)-3-methyl-pyrazolone-5 A 6 D0. 1-(5,7-disulphonaphthyi-2-)-3-methyl-pyrazolone-5 A 6 Do. ..do 1-(3-sulphophenyl)-3-methyl-5-aminopyrazole A 6 Do. 1,4-dia1minobeirazene-3- 2-amino-8-hydroxynaphthalene-fi-su1phonicacid A 44.5 Red.

su p onic ac .-do 2-acetylarnino-5-hydroxynaphthelene-7-sulphonic acid-.." A 6-7 Scarlet. 46 do 1-acetylamino-5-hydroxynaphthalene-7-sulphomcacld..... B 6-7 Red.

EXAMPLE 47 at 30-40 C. Fabrics of cellulose materials can be dyed 51.6 parts of the dyestuff of the formula naphthalene-7-sulphonic acid in water/pyridine in the 50 presence of sodium carbonate and subsequent treatment or printed with this dyestuff by one of the methods described above in ruby shades fast to wet processing, rubbing and light.

In the following Table there are listed the heavy metal complexes of further aminoazo dyestuffs and the reactive components linkable to the amino group, as well as the shades of these dyestuffs on cellulose materials. The preparation of the aminoazo dyestuffs and their metal complexes and the reaction thereof with the reactive components can be carried out in analogy with the instructions of Example 47.

Abbreviations for reactive components as in Table of Example 3 Complex linked Reactive Example heavy comnumber Aminoazo dyestufl metal ponent Shade 1-hydroxy-2-aminobenzene-4,6-disulphonic acid- 2-amino-5-hydroxynaphthalene-7- Cu A Ruby.

sulphonic acid. l-hydroxy-2-aminobenzene-4-sulphonic acid 2-ethylamino-5-hydroxynaphthalene-7- Cu A Do.

sulphonic acid. 1-amino2-hydroxy-6-nitro-naphthalene-4-sulphonic acid 2-amino-5-hydroxynaph On A Do.

thalene-7-sulphonic acid. 51 1-amino-2-hydroxy-6-nitro-naphthalene-4-sulphonic acid 2-amino-5-hydroxynaph- Or A Greenish thalene-7-sulphcnie acid. grey. 52 1-a,mino-2-hydroxy-6-nitronaphthalene-i-sulphonic acid-d-amino-S-hydroxynaph- Co B Reddish thalene--sulphonic acid. black 53 1amino-2-hydroxy-5-methylsulphonyl-benzene-d-amino-B-hydroxynaphthalene-3,6- Cu A Violet.

disulphonic acid. 54 ..do Co A Gre 55 ..do Or A Glgzlaensh ac 56 1-amino-2-mcthylbenzenet-sulphonic acid 1-amino-2-hydroxy-5-methylbenzene-d- Cu B Blue.

amino-S-hydroxynaphthalene-4,6-disulphouic acid. 57 ..do Co B Grey. 58 d0 Cr A Gfienliish ac 59 (l-amino-Z-chlorobenzene-4-sulphonie acid 1-hydroxy-2-acetyiaminobenzcne), Cu A Navy 60 hyidrolysedl-amino-8-hydroxynaphthalene-3,6-disulphonic acid. 0 blue.

n o A Gre 61 1amino-8 hydroxynaphthaleneA-sulphonic acid 1-hydroxy-2,6-diaminobenzene-i- Co A Blagk.

sulphonic acid- 1,S-dihydroxybenzene. 62 1-arnino-8-hydr0xynaphtha1ene-3,6-disulphonic acidi-l-hydroxy-2,6-diaminobcn- Co A Do.

zene-4-sulphonic acid- 2-hydroxynaphthalene. 63 l-amino-8-hydroxynaphthal-i-sulphonic acid l-hydroxy-2,6-diaminobenzene-4- Co A Black.

sulphonic acid-+3-methyl-pyrazolone-(5) 1 7 EXAMPLE 64 96 parts (referred to 100% goods) of the copperphthalocyanine tetrasulphochloride freshly prepared in the usual manner by the reaction of chlorosulphonic acid and thionyl chloride with copper-phthalocyanine, or of the isomeric copper-phthalocyanine tetrasulphochloride synthetised from 1 sulphobenzene-3,4-dicarboxylic acid via the corresponding copper phthalocyanine tetrasulphonic acid, are suspended in the form of the moist, thoroughly washed filter cake in 500 parts of water and 500 parts of ice, a solution of 50 parts 1,3-diaminobenzene in 500 parts of water is added and the pH is adjusted to 8.5 by means of sodium carbonate. The suspension is stirred at room temperature for 24 hours and the pH is constantly maintained at 8.5 by the continuous addition of sodium carbonate. The resultant condensation product is precipitated at pH 1-2 by the addition of sodium chloride, filtered olf with suction, washed and then redissolved neutral in 1000 parts of water. 57 parts 2,4,6-trifluoro-5- chloropyrimidine are introduced into the blue solution with intense stirring, and the mixture is stirred at 20-30 C., while continuously neutralising to pH 6 by means of a sodium carbonate solution, until free amino groups can no Ilonger be detected. The reactive dyestuff of the formu a so obtained is salted out, washed and dried at 30-40 C. in a vacuum. It is a dark-blue powder which dissolves in water to give a blue colour and dyes cotton and regenerated cellulose by one of the dyeing or printing processes described above in clear blue shades of good fastness to wet processing, rubbing and light.

Instead of the 96 parts copper-phthalocyanine tetrasulphochloride, there may be usedin a process which is otherwise the same as in Example 64-87 parts (referred to 100% goods) of the copper-or nickel-phthalocyanine trisulphochloride obtained by the reaction of chlorosulphonic acid with copperor nickel-phthalocyanine, in the form of the moist filter cake thoroughly Washed with icewater; reactive dyestuffs deying in clear blue shades are then likewise obtained.

By working as described in Example 64, but starting from 87 parts copper-phthalocyanine trisulphochloride and replacing the 50 parts of the sodium salt of 1,3-diaminobenzene-4-sulphonic acid with 90 parts of the sodi. um salt of 4,4'-diaminodiphenyl-2,2'-disulphonic acid or 90 parts of the sodium salt of 4,4'-diamino-stilbene-2,2- disulphonic acid, there are likewise obtained reactive dyestufis which dye cellulose materials by one of the methods described above in clear blue shades fast to wet processing, rubbing andlight.

If 4, 4", 4", 4""-tetraphenyl Cu phthalocyanine is used as starting material, there is obtained, after sulphochlorination, reaction with 1,3-phenylene diamine and acylation with 2,4,6-trifluoro-5-chloropyrimidine, a reactive dyestuif which dyes cellulose materials in the presence of acid-binding agents in clear green shades fast to wet processing and light.

EXAMPLE 65 63 parts 1-amino-4-(4'-aminophenyl) amino anthraquinone-2,5,8-trisulphonic acid are dissolved in 630 parts of water, the solution is adjusted to pH 6 by means of a sodium hydroxide solution, 18 parts 2,4,6 -trifiuoro-'5- chloropyrimidine are then added dropwise at -5 C. and a pH of 6-6.5 is maintained by means of a sodium carbonate solution. When the reaction is completed, 7 parts potassium chloride are added, the product is filtered off with suction and washed with a 3% potassium chloride solution. The dyestulf which is obtained in the form of blue-green needles is dried in a vacuum at 30-40" C. It presumably has the formula SOQH and dyes cotton in greenish blue shades.

EXAMPLE 66 EXAMPLE 67 0.1 mole of the copper complex compound is dissolved in 3000 parts by volume of water at pH 6 and combined at a temperature of 20-30 C., while stirring, with 16.8 parts by weight (011 mole) 2,4,6-trifiuoro-5- chloropyrimidine, a pH of 6 being maintained by means of a 2N potassium carbonate solution. The mixture is stirred until the condensation is completed, the dyestutf is separated by the addition of a little sodium chloride and isolated. The residue is washed with acetone and dried at room temperature under reduced pressure. A dark powder is obtained, which dissolves in water to give a green colour and dyes cotton by the methods described in Examples 13 in green shades.

A cotton fabric is impregnated with a solution at 20- 25 C. containing, per litre, 25 g. of the above dyestuif and 0.5 g. of a non-ionic wetting agent (e.g. a polyethoxylated oleyl alcohol), 150 g.' urea and 20 g. sodium carbonate. The fabric is subsequently squeezed between two rubber rollers to a moisture content of about After an intermediate drying at 50- 60 C., the fabric is heated at C. for 2 minutes, the dyeing so obtained is thoroughly rinsed with hot water and treated for 20 minutes at the boil with a solution containing, per litre, 5 g. of Marseilles soap and 2 g. sodium carbonate. After rinsing and drying, there is obtained a green dyeing of good fastness to wet processing, rubbing and light.

Clear green shades of good fastness properties are also obtained on materials of cellulose by one of the other dyeing or printing methods described in Examples 1 to 3, 1'8 and 30.

19 EXAMPLE 68 0.1 mole of the paste of the aminoazo compound of the formula which is obtained by coupling the diazonium compound of 6-acetamino-2-aminonaphthalene=4,8-disulphonic acid with 2-hydroxy-naphthalene-3,fi-disulphonic acid, hydrolysis and conversion of the monoazo compound into the copper complex, is dissolved in 2000 parts by volume of water at pH 6.5 and combined with 20 parts by weight 2,4,6-trifiuoro-S-chloropyrimidine. The reaction mixture is stirred at 20-30 C. until the condensation is completed, the pH of the reaction solution being maintained at 6-7 by the addition of a sodium carbonate solution. When the reaction is completed, the dyestutf is salted out, isolated and dried in a vacuum.

The dried dyestufi is a dark powder which dissolves in water to give a violet colour and dyes cotton in the presence of alkali in bluish violet shades.

EXAMPLE '69 An aqueous solution of 0. 1 mole of the copper complea of the formula nois (|)Ou0 HIN g 03H s 03H chloropyrimidine. A pH of 6-7 is maintained by the addition of sodium carbonate and when the reaction is completed, the dyestuif is isolated by salting out. In the dry state the dyestutf is a dark powder which dissolves in water to give a violet colour. Cotton fabric is dyed in violet shades fia'st to light and wet processing.

EXAMPLE 27.5 parts of the sodium salt of Z-methylamino-S- hydroxy-naphthaleneJ-sulphonic acid are dissolved in 150 parts of water, 20 parts 2,4,6-trifluoro-S-chloropyrimidine are added and the mixture is stirred at 30 C., while continuously neutralising the hydrogen fluoride formed to pH 6-7 by means of a total of 34 parts by volume of a 16% sodium carbonate solution. After a short time, the acylation is completed, the pH is 6 and changes no more.

30 parts sodium bicarbonate are then added, and a diazo suspension from 34 parts of the disodium salt of Z-aminonaphthalene-1,7-disulphonic acid in 200 parts of water is added dropwise at 20 C. within 15 minutes. The orange-coloured reactive dyestufi of the formula SIOaNB OH NaOaS N=N NEO S which is immediately formed, is completely separated, after further stirring for one hour, by means of parts sodium chloride, filtered off, washed with a dilute sodium chloride solution and dried at 35 C. in a vacuum. The dyestutf dyes cellulose materials by the methods described above in reddish orange shades of very good fastness to wet processing and good fastness to chlorine.

Orange to red reactive dyestuffs are obtained in an analogous manner by acylating the aminonaphthol-sulphonic acids stated in Column 3 of the following table with 2,4,6-trifiuoro-5-chloropyrimidine and coupling the resultant acylamino-naphthalosulphonic acids with the diazo components stated in Column 2.

Example Shade on number Diazo component Aminonaphtholsulphonic acid cotton 71 z-amllionaphthalene-1,7-disulphonic 2-ethylamino-5-hydroxynaphthalene-7-sulphonic acid Orange.

do 2-(fl-hydroxyethylamino)-5-hydroxynaphthalene-7-sulphonic acid.... Do. 7'4 do- 2-arnino-5-hydroxynaphthalcne-7-sulphonic acid Do. 7 d0. 2-amlno-5- ydroxynaphthalene-l,7-disulphonic acid 0. 75 do- Z-amino-8-hydroxynaphthalene-6-aulphonic acid Scarlet. 7 do... amino-8-hydroxynaphthalenc-3,6-disulphonic acid-. Do. 77 2-amimnonaphthalene4,5-dlsuiphonic 2-methylamino-5-hydroxynaphthalene-7-sulphonic acid Orange.

ac 78 do Z-ethylamino-5-hydroxynaphthalene-7-sul honic acid Do.- 70 do 2-(B-hydroxyethylamino)-5-hydr0xynapht alene-7-sulphonic acid Do. so do 2-amino-5-hydroxynaphthalene-7-sulphonic acid" Do. R1 d0.. 2-amino 5-hydroxynaphthalene-1,7-disulphonic ac Do. 12 .do 2-amino-8-hydroxynaphthalene-6-sulphonic acid Scarlet. 83 do 2-amino-8-hydroxynaphthalene-S,6-disulphonic acid Do. 84 2-amiionaphthalene-i,5,7-trisulphonic 2-amino-5-hydroxynaphthalene-7-sulphonic acid Orange.

aci 85 do 2-methylamlno-5hydroxynaphthalane-7-sulphonic acid Do. 8 do. 2-amino8-hydroxynaphthalene-G-sulphonic acid Scarlet. 87 Z-aminobenzenesulphonic acid 2-methylamino-5-hydroxynaphthalcne-7-sulphonic acid Orange. 88 d 2-(fl-hydrokyethylamino)-5-hydroxynaphthalene-7-sulphonic acid...- Do. 89-... 2-amlno-8-hydroxynaphthaiene-6-sulphonic acid Scarlet. 90 2-amino-8-hydroxynaphthalene-3,6-disulphon.ic acid. Do. 91-.- d0 2-a'min06-hydroxynaphthalene-1,7-disu1phonic acid. Orange. 92 Z-amInonaphthaIene-l-sulphonic acid.- l-amino-B-hydroxynaphthalene-3,6-disulphonic acid. Blulsih 1'6 93 do l-amino-8-hydroxynaphthalene-4,6-disulphonic acid. Do. 94 Z-anriaronaphthalone-1,5-disulphonic l-amino-S-hydroxynaphthalene-Iifi-disulphonic acid.. Do.

ac 95 1amino-841ydroxynaphthalenet,fi-disulphonic acid Do. 96 do l-amino-S-hydroxynaphthalene-G-sulphonlc acid Do 97 2-arr iionaphthalene-1,7-disulphonio 1-amino8-hydroxynaphthaleneq'iedisulphonic acid Do. 98 .do l-amino-8-hydroxynaphthalene-4,6-disulphonic acid Do. 9 .do 1-amino-8-hydroxynaphthalene-d-sulphonic acid Do. 100 2-anginonaphthalena-1,5,7-trisulphonic do Do.

ac 101 l-arnno-i-chlorobenzene-Mulphonic l-amino-S-hydroxynaphthalene-3,6disulphonic acid Do.

ac 102 z. 1-amino-2-mcthoxybenzene5- do- Do.

sulphonic acid. 103 l-ammo-bcnzene-Z-carboxylic acid-4- do.... Do.-

sulphonic acid. 104 1-amino-4-acety1aminobenzene-2- do Violet.

sul honic acid. 105 0.-. A l-amino-S-hydroxynaphthalone-4,6-disulphonic acid Bluish red.

21 EXAMPLE 106 56.8 parts of the diamino-azo dyestufi obtained by coupling diazotised 1-amino-S-acetyl-aminobenzene 6 sulphonic acid with Z-aminonaphthalene-5,7-disulphonic acid in an acetic acid medium and subsequent alkaline or acidic 22 pyrimidine and the mixture is stirred at 30 C. for one hour, a pH of 6 being maintained by the continuous addition of a sodium hydroxide solution. The acylation product which is partially precipitated is completely separated at pH 7 by the addition of 100 parts sodium chlohydrolysls of the acetylammo group are dissolved at PH ride and filtered ofi. For purification, the reactive dyestulf 7 in 5 parts f water After the addition of 20 parts so obtained can be redissolved in 2500 parts of water z,46 trifluom 5 ch1orpyrimidine, the mixture is Stirred at 30 C. clarified and separated again by salting out the at C. for about one hour, while continuously new filtrate with 350 parts sodium chloride. The dyestuff has tralising the liberated hydrofluoric acid to pH 6-7 by 10 the formula means of a sodium carbonate solution. When the acylation so @Na F is completed, the resultant reactive dyestutf which pre- N sumably corresponds to the formula SOaNB NH2 Na0;S- SO Na NH-COCH] (El 1'' I after filtering ofl, drying at 35 C. and grinding, it is a HN a yellow powder which readily dissolves in water to give I a yellow colour and dyes cellulose fibres by one of the M1018 dyelng methods described above in the presence of acidis Salted out, filt r d ff redissolved in 4000 parts of binding agents in very fast redd1sl1 yellow shades. Fast water at C., filtered and separated from the filtrate in yellow Shades are also Obtalned 1 01 and polyamide completely pure form by the addition of 400 parts sodium chloride. The dyestutf is dried as usual at c. in a 25 slmllar dyestuffs are Obtamed y followmg the p vacunm. It dyes cellulose materials by one of the methods cedflre descnbed reP1a1I1g the P ts of the described above in fast yellowish orange shades. Sodlum salt of 4 P' 'P Y LE 107 naphthalene-(2)-3, 6,8-trisulphomc acid with correspond- EXAMP mg amounts of the aminoazo dyestulfs obtained from A neutral solution of 60 parts of the trisodium salt 30 e ammo compounds Stated in Column 2 and the conof the aminoazo dyestutr' obtained by coupling diazotised p g c mponents stated 1n Column 3 in the usual man- Z-aminonaphthalene 3,6,8 trisulphonic acid with 3- ner by diazotisation and coupling in an acetic acid meacetylaminoaniline in an acetic acid medium, in 500 parts (hum, and acy g W131 py of water is admixed with 20 parts 2,4,6-trifluoro-5-chlorodine.

Example number Diazo component p ng component Shade on cotton 103 2-aminonaphthalene-1,fi-disulphonic acid l-amin0-3-methyl-6-methoxybenzene Strongly reddish B 0 109 do i-amino-Zi-methylbenzene Yzllow f 110.... -do. i-aminonaphthalene fi-sinphonie acid Reddish yellow. 111 do l-amindS-acetsrlaminobenzene 112 do 3-aminophenyl-urea D 113 .do l-amino-S-hydroxyacetylamin 11 2-aminonaphthalene-5,7-disulphonic acl l-amino-3-methyl-fi-methoxy-benzene Stroflgly reddish ye 0W- l-amlnonaphthalene-7-sulphonic acid Reddish yellow. l-amino fi-acetylaminobenzene D 3-aminophenyl-urea D 1-arnlno-3-hydroxyacetyiaminobenzene Do. i-amino-a-methyl-fi-methoxybenzene Strofigly reddish ye OW- 1-amino-3-methylbenzen8 Reddish yellow. l-aminonaphthalene-fi-sulphonic acid. Reddish yellow. l-amino-s-methylbenzene Do. 1-amino-Zl-methyl-S-methoxy-benzene strolrigly reddish ye 0W.

l-amino-(l-acetylaminobenzene Reddish yellow.

il-amlnophenyl-urea Do. l-amino-tl-hydroxyacetylamin 11 Do. i-aminonaphthalene-d-sulphonic acid- Do. 1amino-3-acety1aminobenzene Do. 1-amino-2-methoxynaphthalene-tl-sulphonic acid Stmflgly reddish ye 0W. do i-aminonaphthalene-B-sulphonic acid Reddish yellow. 131 2-aminonapl1thslene-4,8-disnlphonic acid ..do ellow. 2 d l-aminonsphthalene-7-sulphonlc acid Do. 133- do l-amino-z-methoxynaphthalene-6-sulphonic acid Stro gly reddish ye GW- 134 do l-methylamino-a-methylbenzene..a Yellow. 135 2-aminonaphthalene4,S-disulphonic acid 1-ethylamino-3-methylbenzene.. Do. 13 o N-methyl-a no Do. 0..... N'ethylaniline D0. 0 N-(fl-hydroxyethyD-am e Do. .0 N-butyl-a ne Do. 2-amin0n8phthalene-3, Reddish yellow. 141 do 1arnino-8-methylbenzene Do. 142 do-.. 3-eminophenyl-urea..... Do. 143 do.... 1-amino-3-hyd.roxyacetyl Do. 144 o 1-amino-3-aeety1amino-6-methoxybenzene Yellowish orange. 145 do l-amino-3-acetylamino-fi-methylbenzene Reddish yellow. 146... do 1-e.mino-3-methane-sulphonylsminobenzene Do. 147 do 2,5-div yaniline.-. Yellowish orange. 148 do S-methyl-dmethoxy-nniline Do. 149 do N-methyl-aniline Reddish yellow. 150 do N-ethyl-anil'lnn Do, 151 do N-butyl-aniline D0. 1R2 do N-(B-hydr0Xyethyl)-anilino D0. 153 do 3-(N-etl1ylamino)-toluene Do. 1K4 do 2-aminotolu na Do.

TABLEContinued Example number Diazo component Coupling component Shade on cotton W ..do 1-amlno-2,5-dlmethy1b m n StIOilIZIY reddish ye ow. 156 ..do l-amino-Z-methoxybenzene. 0.

(1n 1-amino-3-methoxybenzene Reddish yellow. (in l-ethylamino-3-methoxy Do. 1-aminonaphthalene-G-sulphonic acid Do. 160 ..do l-aminonaphthalene-7-sulphonic acid.. Do. 161.. 2-aminonaphthalone-4,6,8-trisulphonic acid.. 1-amino3-methylbenzene Do. 162.. do 1-amin0-3-acetylaminobenzene Do. 1 1-aminonaphthalene-2,4,7-trisulphonic acld.- Yellow. 1 d l-amiuonaphthalene-ti-sulphonic acid Do.

-4-aminostilbene-2,2-d.isulphonlc acid 1-amino-3-acetylaminobenzene....--. Reddish yellow. d 3-amlnophenyl-urea D0. 1-amino-3-hydroxyaoetylaminobenzene Do. N-methyl-aniline Do. N-ethyl-aniline-.- Do. N-butyl-aniline.. Do. N-(B-hydroxyethyD-anihne Do. l-(N-ethylarnino)-3-methylbenzene.. Do. 173... l-aminonaphthalene-o-sulphonic acld-- Do. 174... l-aminonaphthalene-7-sulphonic acid.. D0. 175 l-amino-li methylbenzene Yellow. 176 1-amino-3-acetylaminobenzene... Do. 177 1-amino-2-methoxy-5-methylbenzene Reddish yellow. 178... ...do 1-arnino-2,5-dimethoxybenzene D 179 niline-2,4-disulphonic acid 1-emino-2-methoxy-5-methylbenzene Reddish yellow.

EXAMPLE 180 65 parts of the dyestufi of the formula (prepared by coupling diazotised l-hydroxy-Z-aminobenzene-4,6-disulphonic acid with 2-arnino-8-hydroxynaphthalene-6-sulphonic acid and coppering the resultant azo dyestuff) are dissolved neutral in 700 parts of water. 20 45 parts 2,4,6-trifluoro--chloropyrimidine are added and the mixture is stirred at -30 C., while continuously neutralizing the liberated acid to pH 6-7 by means of a sodium carbonate solution, until free amino groups can no longer be detected. The resultant reactive dyestufi' of the formula is salted out, filtered off, washed and dried at BO- C. The dyestuif dyes cellulose materials by one of the methods described above in very fast ruby shades.

Dyestuffs with similar properties are obt aincd in analogy with the method described above from the copper complexes of the azo dyestuffs prepared from the diazo and azo components stated in the following Table:

Shade on Number Diazo component Coupling component m 181. 2-methylamino-5hydroxynaphthalene-7-sulphonic acid. 182. 2-ethylamino'5-hydroxynaphthalene-7-sulphonic acid. 183. 2-(fl-hydroxyethylamino)-5-hydroxynaphthalone-7-sul 184. 2-amino8-hydroxynaphtha1ene-3,6-disulphonic acid 185. 2-amino-S-hydroxynaphthalene-l,7-dlsulphonic aci 186. 2-amlno-8-hydroxynaphthalene-3,6-disulphonic acid- 187. 2-methylamino-5-hydroxynaphthalene-7-sulphonlc a 188... 2-ethylamino-5-hydroxynaphthalene-7-sulphcnic acid 189.. 2(B-hydroxyethylamino) -5-hydroxynaphthalene-7-sulphonlc acid Do. 190..- 1amino-8-hydroxynaphthalene-3,Miisulphonlo acid- Violet. 191... l-amino-S-hydroxynaphthalone-4,6-disulphonic acid- Do, 192... l-am1no-8-hydroxynaphthalene-3,6-disulphonic acid- Do. 193... ..do l-amino-S-hydroxynaphthalene-4,6-disulphonic acid. Do. 194 1.hygroxy-2-amino-4acetylamlnobenzene-(i-sulphonlc 1-amino-8-hydroxynaphthalene-ibfidisulphonic acid Bluish aci violet. 195 do 1-etl1oxy-8-hydroxynaphthalene-3,6-disu1phonlc acid Do.

(i-positioned aoetylamino group subsequently hydrolysed) 196 1-hydiroxy-2-amino-4-acetylaminobenzene-o sulphonic l-aminol-hydroxynaphthalene-2,4-disulphonic acid Blue.

aci 197 do- 1-amino-8-hydroxynaphthalene-2,4,6-trisulphonio acid Do. 198 l-hyirtllroxy-2-amino-oacetylaminobenzene-4-sulphonic 1-amino-8-hydroxynaphthalene-2,4-disulphonie acid Do.

(ti-positioned aeetylamino group hydrolysed) 199 1-amino-2-hydroxy-G-nltronaphthalene-4-su.lphonie acid.- 1amino-8-hydroxynaphthalene-2,4-disulphonie acid Do.

(ti-positioned nitro group subsequently reduced to N H 200 l-amlno-2-hydroxy-o-nitronaphthalene-4-sulphonic acid.. I-amiuo-SFhydrOxynaphthalene-2,4,6-trlsulphonic acid Do.

(ti-positioned nitro group subsequently reduced to --NH' 201 l-hydfoxy-Z-amino-fi-acetylammobenzene-i-sulphonic l-amino-S-hydroxynaphthalene-2,4,6-trisulphonic acid Do.

(G'posltioned acetylamlno group hydrolysed) 25 EXAMPLE 202 The procedure is as described in Example 30 but the diazotised reactive group-containing intermediate is coupled in a soda-alkaline medium, instead of vn'th 47 parts of the sodium salt of 1-benzoylamino-S-hydroxynaphthalene-3,6-disulphonic acid, with 40 parts of the sodium salt of 1 acetylamino8-hydroxynaphthalene-3,6-disulphonic acid, and the resultant dyestuif of'the formula SOiNB is isolated in the manner described in Example 30. The water-soluble dyestuif dyes cellulose materials by the padsteaming or pad-thermofixing method (at 140 C.) in bluish red shades which are white dischargeable and fast to rubbing and light.

EXAMPLE 203 A solution of 19.5 parts of the sodium of l-aminobenzene-4sulphonic acid and 6.9 parts sodium nitrite in 200 parts of water is poured into a mixture of 100 parts of ice and 28 parts by volume of concentrated hydrochloric acid; the reaction mixture is then stirred for id hour at -10 C., and the excess nitrous acid is subsequently removed. The diazo suspension so obtained is admixed at 0-10" C. with a cooled and thereby partially crystallised solution of 26.2 parts of the potassium salt of l-aminonaphthalene-S-sulphonic acid in 250 parts of hot water and the strongly acidic coupling mixture is neutralised at 10-20 C. to pH 4 by the careful addition of a sodium hydroxide solution. The coupling is rapidly completed; the aminoazo dyestuif formed is completely salted out with 100 parts sodium chloride, filtered oil? with suction, washed and redissolved in 500 parts of water at 10 C. and pH 6-7. The aqueous solution is mixed dropwise with 20 parts 2,4,6-trifiuoro-5-chloropyrimidine and stirred at 20- 30 C., while continuously neutralising the liberated acid to pH 6-7 by means of a sodium carbonate solution. When the aminoazo dyestutf can no longer be detected, the reactive dyestuif of the formula which is partially precipitated, is salted out with 40parts sodium chloride, filtered off and redissolved in 800 parts of warm water for purification. After clarification of the solution, the pure dyestuif is separated from the filtrate by the addition of 80-100 parts of sodium chloride. After filtering off, drying at 35 C. and grinding, there is ob- 2 nents stated in the following Table are coupled with laminonaphthalene-8-sulphonic acid, then valuable yellow to brown reactive dyestufis are likewise obtained after acylation with 2,4,6-trifluoro-5-chloropyrimidine.

Mainline-2-acetylamino-azobenzene-Z, 5'-disuiphonie Orange-brown;

? OINB Rcddish brown.

S OiNa S OaNa (1-aminobenzene-2,5-disulphonic acid coupled in an acigiic medium with l-amino-naphthalene-6-sulphonic ac S OaNa (i-arninobenzene'z 5-disuiphonic acid coupled in an acidic medium with the technical mixture oi l-aminonaphthalene-fiand -7-suiphonic acid).

S OIN8 QM NH.

(1-amino-naphthalene-2, 5, 7-trisulphonic acid coupled in an acidic medium with Lamina-naphthalenefi-sulphonic acid).

MQNH. N30: S- H:

S OINa (l-amino-naphthalene-2,5,7-trisulphonic acid coupled in an acidic medium with 1-amino-2-methoxy-5- methylbenzene).

Violet-tinted brown.

Reddish brown.

EXAMPLE 204 When a cellulose fabric is printed with a printing paste which contains, per kilogram, 30 g. of the dyestulf described in Example 18, g. urea, 300 g. of water, 500 .g. of alginate thickening agent (60 g. sodium alginate per kilogram thickening agent), 10 g. sodium carbonate and 10 g. of the sodium salt of 3-nitrobenzene-sulphonic acid and which has been made up with water to 1 kilogram, the fabric is subsequently subjected to an intermediate drying and then steamed in a suitable steaming apparatus at 103 to C. for 30 seconds, a bluish red print of good fastness to wet processing, rubbing and light is obtained after rinsing and soaping at the boil.

EXAMPLE 205 A mixture of the solutions of 65.5 parts each of the 27 chromium 2:1 complex and the cobalt 2:1 complex of the dyestuff of the formula 28 chloro-5'-sulphophenyl) 3 methyl-pyrazolone-(S) and subsequent reduction of the nitro group with sodium sulphide, in 300 parts of water is admixed with 20 parts OH HO NH:

l l 2,4,6-trifluoro-S-chloropynmrdine, and the mixture is N=N stirred at 30 C. for one hour while the liberated acid is 5 continuously neutralised to a pH value of 6.0 by means of M035 soaNa a sodium carbonate solution. The precipitated dyestufi of the formula SOaNa F $03Ma each in 400 parts of water, is stirred with 40 parts 2,4,6 trifiuoro-S-chloropyrimidine at 30-40 C. for about 2 N/ N=N-CCCH: hours while maintaining a pH of 6-7. When no more n aminoazo dyestulf can be detected by chromatography F (Co-complex: blue; Cr-complex: blue-green), the resultant mixture of the two reactive dyestuffs is salted out with Cl potassium chloride, filtered off and dried.

The dyestuif yields on cellulose materials by the pad- N80 S dyeing processes or when printed in the presence of acid- I g ggz igsg sgs gf shades of very good fasmess is filtered off, dissolved warm at pH 6-7 in 3000 parts of valulgbl blaci d t ff a l bt d b d water, and reprecipitated from the filtered solution by the in male i 1 b 5 zi h V P addition of sodium chloride. After filtering olf, drying and 0b u i i' e c rPmmm pulverising, there is obtained a yellow powder which is St a comp exes o t e o owmg ammoazo readily water-soluble and dyes cellulose materials from a u long bath at 30 C. or by the cold batch padding process with sodium carbonate as acid binding agent in clear yel- C9ulow shades fast to washing, rubbing and light. 111mg 1 m component Coupling component pH Va uable new reactive dyestuffs are also obtained by following the procedure described above but replacing l-h drox -2 mino-l-nit 1-h d n n a to eie-iifiziifiifiifiinl gigi 9 the aminoazo dyestuff there used with equ1valent amounts 1-hydrozy-2-amlno-4-nltro- .do 9 naphthaleneqmphomc of the ammoazo dyestuffs synthetised from the compo acid. nents stated 1n the following Table.

In the Table the term hydrolysed means that an lamino group contained in the aminoazo dyestuff was XA acy E MPLE 206 subsequently hydrolysed, while the term reduced indi- A neutral solution of 53.15 parts of the disodium salt cates that a nitro group contained in the diazo compoof the aminoazo dycstulf obtained by coupling diazotised nent is reduced after the coupling to the amino group, 1-amino-4-nitrobenzene 2 sulphonic acid with 1-(2'- whereby the desired aminoazo dyestuif is formed.

pH of Example coupling Shade on number Dlazo component Azo component medium cellulose 207 l-amino-d-nitrobenzene-2-sulph0nic acid 1-(4'-sulphophenyl)-3-methyl-pyrazolone-(5) 5-6 Yellow.

(i-positioned nitro group subsequently reduced). 208 ..d0 1-(4 -sulphophenyl)-3-earboxy-pyrazolone-(5) 5-6 Redldish ye 0W 209 .-do 1-(3-sulphophenyl)-3-methyl-5-amino-pyrazole 6-7 Yellow. 210 1-amino-3-acetylamino-benzene-G-sulphonic acid .-do 6-7 Do.

(ti-positioned acetylamino group subsequently hydrolysed). 211 -d0 1-(fl-hydroxyethyl)-3-methyl-pyrazoione-(5) 5-6 Do. 212 -.2 moles l-amino-3-acetyl-amlnobenzene-c-sulphonic 1 mole bis-pyrazolone from 4,4-bishydrazino-dlbenzyl-2,2- 5-6 Do.

acid (hydrolysed). disulphonic acid and acetoacetic ethyl ester). 213 1 mega (ll-laninp-ii-agftyl-aminobenzene-o-sulphonic 1-(4'-sulphophenyl)-3-carboxy-pyrazolone-(5) 5-6 Do.

801 y 0 yse 214 1-amino-5-acetylamino-naphthalene-3,7-disul- 1-(4-sulphophenyl)-3-carboxy-pyrazolone-(5) 5-6 Beddish phonic acid (hydrolysed). yellow. 215 l-amino-2-methylbenzene-4,6disulphonic acid--... 2-acetylamino-S-naphthol-7-sulphonie acid (hydrolysed)..- 78 Orange. 91!; rln 2-acetylamino-8-naphthol-fi-sulphonic acid (hydrolysed)..- 7-8 Red. 217 1-amino-2-methylbenzene-4,6-disulphonic aeid.-..- 1-c(hhloi("fi-2]-aceylamino-5-naphthol-7-sulpl1onic acid 7-8 Orange.

y o yse 218 l-aminobenzene-Z-sulphonlc acid 1-a(cgt3( 1lra1ilin%-hydroxy-naphtha.lene-4,6-disulphonic acid 7-8 Red.

y 0 yse 219 2-aminonaphthalene-3,6-disulphonic aciddo 7-8 Bluish red. 220- Z-aminonaphthalene3,7-disu1phonic acid.-- 7. 8 Do. 221... 2-aminonaphthalene-4,8-disulphonic acid..-- do 7-8 Do. 222 Z-aminonaphthalene-3,6-disulphonlc acid l-aaetglarfiinrgf-hydroxynaphthalene-dfi disulphomc acid 7-8 Do.

y o yse 223 2-aminonapnthalene-4,8-dlsu1phonic acid l-afietglaifiimgyhydroxynaphthalene-3,6-disulphonic acid 7-8 Do.

y o yse 224 l-amino--methoxy-benzene-Z-sulphonic acid 2-(N-acetyl-N-methylamino)-5-hydroxynaphthalene-7- 7-8 Yellowlsh sulphonic acid (hydrolysed). red. 225 do 2-(N-acetyl-N-methylamino)-8-hydroxynaphthalene4i 7-8 Red.

sulphonic acid (hydrolysed). 226... 1-aminobenzene-2-sulphonic acid.. 2-(N-acetyl-N-methylamino)-8-hydroxynaphthalene-6- 7-8 Red.

sulphonic acid (hydrolysed). 227. 1-aminobenzene-3-sulphorucacid.. do 7-8 Red. 228. l-amlnobenzene-i-sulphonic acid-.. do 7-8 Red. 229. 1-amino-4-methylbenzene-2-sulphonic acid dn 7-8 Red. 230- 1-amino-2,4-dimethylbenzene-B-sulphonic arid do h 7-8 Red. 231 do 2-agletylraxiuino-8mydroxynapthaleneo-sulphonlc acid 7-8 Red.

y o yse 232 do. 2-a4etglaFino-8-hydroxynaphthalene-3,6-disulphonic acid 7-8 Red.

y o yse 233 i-aminoazobenzene-3,4'-dlsulphonic acid i-amlnda-acetylaminobenzene 5-6 Yelllowrown do 1-amino-3-hydroxy-acetylaminobonzene 5-6 Do. 235 do l-amlno-naphthalene-S-sulphonic aeid.-.. 5-6 Do. 236 do l-amino-naphthalene-7-sulphonic acid 5-6 Do. 237 do l-amino-2-(4-amino-2'-sulphophenyl-(1)-azo)-8-hydroxy- 8 Black.

naptha1ene-3,6-disulphonic acid.

29 EXAMPLE 238 wet processing and good fastness to light are obtained on cotton.

The dyestuif obtained presumably corresponds to the formula O NH:

I S 03H N l NH -cH,N N

Example number Water-soluble amino-anthraquinone derivative Shade 240 1-amino-4-(4-N-methylaminomethy1auilino)-anthraquinone-2,6,2'-trlsulphonlc acid. Greenlsh blue. 241-. 1-amino-4-(4-N-methylaminomethylanillno)-anthraquinone-2,5,8-trlsulphonic acid. Do. 242.. 1-amino-4-(4-N-methylaminomethylanilino)-anthraquinone-2,8-dlsulphonic acid- Blue. 243...- l-amino-4-(4'-aminoanilinc)-anthraquinone-2,6-disulphonic acid Blue-green. 244..-. 1-amino-4-(4'-aminoanilino)-anthraquinone-2,5-disulphonic aci Greenish blue. 245.. l-amino i-(3-amlnoanili.uo)-anthraquinone-2,6-disulphonic acid- Blue. 246-. 1-amino-4-(3-amin0anilino)-anthraquinone-2,5-disul honic acid Do. 247.. 1-amin0-4-(3-aminoani1lno)-anthraquinone-2,4-dlsu phonic acid.. Somewhat reddish 1 ue. 248 l-amlno-t-(If-aminoanilino)'anthraquinone-2,4-6-trisulphonic acid Reddish blue. 249 1-amino-4-(4'-aminoeyclohexylamino)-anthraquinone-2,5,S-trlsulphonic acid- Clear blue. 250.. 1-amin0-4-(4-N-methylaminomethyianil1no)-anthraquinone-2,3-disulphonie acid Blue. 251.. 1-amino-4-(4I4"-aminobenzoy1amino]-an1lino)-anthraquinone-2,5,S-trisulphonic aci Blue-green. 252..

SOaH

(1 1-amino-4-(4'-[4"-aminobenzene-sul honamido]-anilino)-anthraquinone-2,5 S-trisulphonic acid" Greenish blue. 1-am1no-4-(4-aminost1lbene-amlno -antl1raquiuone-2,2,2"-trisulphonic acid G reen.

Clear reddish blue.

s OzNH- s Or-Q-NH: Ha

2,4;6-trifluoro-5-chloropyrimidine at -30 C. for one hour. The liberated acid is continuously neutralized to a pH value of 5.5-6 by means of sodium carbonate. The resultant reactive nitro dyestuif of the formula aNa is salted out, filtered oif, washed and dried. It dyes cellulose fibres from a long bath or by one of the usual padding methods in the presence of sodium carbonate as acidbinding agent in deep violet-brown shades fast to wet processing and rubbing.

EXAMPLE 239 52 parts l-amino-4-(4-N-methylamino-methylanilino)- anthraquinone-2,2'-disulphonic acid are dissolved in 550 parts of water and the solution is adjusted to pH 6 by means of a sodium hydroxide solution. 18 parts 2,4,6-trifluoro-S-chloropyrimidine are then added dropwise at room temperature and a pH of 6 is maintained by means of a 2N sodium carbonate solution. The reaction is observed chromatographically. The reaction product which crystallises in the form of blue needles is filtered off with suction and the filter residue washed with a 3% sodium chloride solution. Clear blue dyeings of good fastness to EXAMPLE 255 When proceeding according to the instructions of Example 18, 'but coupling the resultant dyestuif intermediate, instead of twith the diazo compound from 17.5 parts Z-amino-benzene-sulphonic acid, with the diazo compound from 20.8 parts 3-chloroaniline-6-sulphonic acid in the presence of 12 parts sodium carbonate at a final pH of 7, then there is obtained a reactive dyestul'f of the formula F some no NH- N \N N=N c1 1 NaO;S some dyed or printed, preferably in the presence of sodium carbonate, in the stated shades:

Example Coupling number Diazo component Coupling component H Shade 256 1-amino+methoxybenzene-G-sulphonic acid l-amino-S-hydroxynaphthalone-3,6-disulphonic acid 7-8 Violet. 257 do 1-amino-8hydroxynaphthalene-4,6-disulphonic acid 7-8 Rtartiidlis'h e 258 ..do 2-amino-5-hydroxynaphthalene-l,7-disulphonic acid 7 Scarlet. 259...- 1-amino-5-ehlorobenzene-2-sulphonic acid d0 7 Orange. 260.... l-aminobenzene-S-sulphonic acid- 0-.- 7 Do. 261--.. l-aminobenzene-4-sulphonic acid ..do 7 Do. 262.. ....do 2- mino 8-hyd1oxynaphthalene-(i,6-disulphonic acid 7-8 Scarlet. 263.. d-aminobenzoic acid-(p-sulphoothyD-amide 1-amino-8-hydroxynaphthalcne-ikfldisulphonic acid 7-8 Red. 264.. l-amiio-4-sulphoacetylarnino-benzene-Gsulphonic .....do 7-8 Violet aci 265.. l-aniino-ii-sulphoacetylaminmbenzene-dsulphonic 2-amlno-5-hydroxynaphthalone-1,7-disulphonic acid. 7 Orange.

ac 266.. l-amino-4-sulphoacetylaminobenzene 2-amin0-5-hydr0xynaphthalene-1,7-disulphonic acid 7 Scarlet. 267 1-aminobenzene-2,4-disulphonic acid 11(2-n2hyl-3'-an1ino-5'-sulphophcnyl)-3-methylpyraz- 6 Yellow. 0 one- 268 2-amino-naphtl1alone-4,8disulphonic acid do-.- 6 Do.

EXAMPLE 269 EXAMPLE 279 When proceeding according to the instructions of Ex- 58 parts of the dyestuflf of the formula ample 30, but coupling the dyestutf intermediate obtained from 1,3-diaminobenzene-G-sulphonic acid and 2,4,6-tr1- fluoro-S-chloropyrimidine, after diazotisation at 10 C. J -O and pH 7.5 to 6.5 with a solution of 40.5 parts of the disodium salt of 2-sulphoacetylamino-S-hydroxynaphthal- N -CH: ene-7-sulphonic acid, then there is obtained a reactive dyestuff of the formula Naoas Nfloas 503E OH F N (prepared by coupling diazotised 1 hydroxy-2-amino-4- N chlorobenzene-S-sulphonic acid with 2 methylamino-8- Hols hydroxynapthalene-6-sulphonic acid and coppering the re- 40 sultant azo dyestuff) are dissolved neutral in 700 parts of which dyes cellulose materials by one of the usual methods of application with sodium carbonate as acid-binding agent in fast orange shades.

EXAMPLE 270 When the procedure described in Example 206 is followed but, instead of the amionoazo dyestuff there used, 53.15 parts of the disodium salt of the amino azo dyestuif obtained by coupling diazotised 1-amino-4-nitrobenzene-2-sulphonic acid with 1-(2-chloro-5-sulphophenyl)- 3-methyl-pyrazolone-(5) and subsequent reduction of the nitro group with sodium sulphide, are acylated with 2,4,6- trifiuoro-S-chloropyrimidine, then a valuable reactive dyestufi is also obtained, with which cellulose materials can be printed in fast yellow shades by the usual dyeing or printed methods.

Similar reactive dyestuffs are obtained, when, instead of the aminoazo dyestufl mentioned above, one on the aminoazo dyestuffs synthetised from the components stated in the following Table is acylated with 2,4,6-trifluoro-S-chloropyrimidine.

water. 20.0 parts 2,4,6-trifluoro-5-chloro pyrimidine are added dropwise and the mixture is stirred at 20-30 C., while continuously neutralising the liberated hydrofluoric acid to pH 6.0-6.5 by means of a sodium carbonate solution, until free amino groups can no longer be detected. The resultant reactive dystufi' of the formula 0 911-0 F I l NaOaS Example number Dlnzo component Azo component Shade 271 l-amino-i-nitrobenzene-2-sulphonic acid (reduced) 1-(2'-methyl-4'-sulphophenyl)-3-methyl-pyrazolone-(5) Yellow. 272 do 1-(2',5disulphophenyl)-3-methyl-pyrazolone-(5) Do. 27a (in 1- I'-meEg)yl-4-sulpho-6-ehloropheny1)-3-methylpyraz- Do.

0 one- 274 1-amino-4-nitrobenzene-2-sulphonic acid (reduced) 1-(2',5 -dichloro-4'-sulphophenyl)-3-methylpyrazolone-(5) Do. 275 banging-33cctylaminobenzene-o-suplhomc 801d (hy- 1-(2-methyl-4'-sulphophenyl)-3-methyl-pyrazolone-(5)..... Greenish yellow. 276 do 1- 'sulphophenyl)-3-methyl-pyrazolone-(5) Do. 277 do 1-(2'-methyl-4sulghophenyl)-3-carboxy-pyrazolon Do. 272 do 1-(2-chloro-4-sulp ophenyl)-3Fcarboxypyrazolone-(5) Do.

EXAMPLE 293 62.0 parts of the trisodium salt of the dyestuff obtained by soda-alkaline coupling of diazotised 4-chloro-2-aminol-hydroxybenzene with 1 amino-8-hydroxynaphthalene- 3,6disulphonic acid are mixed in 300 parts at 70-80 C.

and a pH of 8-9 with 54.2 parts of the 1:1 chromium 30 complex of the dyestufi obtained from 6-nitro-1-diazo-2- hydroxynaphthalene-4-sulphonic acid and 2-hydroxynaphthalene. A deep blue solution has formed after 10 minutes.

The mixed complex is acylated within about 1 hour at 30-40" C. and a pH of 6.5-7.5 with parts 2,4,6-triiluoro-S-chloropyrimidine. During this operation the pH value is kept constant by the dropwise addition of a sodium carbonate solution. The acylated dyestuif is separated by means of 20% sodium chloride, filtered ofi with suction and dried at C.

A blue-black print of excellent fastness to light and washing is obtained on cotton by the method described in Example 3.

EXAMPLE 294 30.4 parts 2-amino-8-hydroxynaphthalene-3,6-disulphonic acid are dissolved neutral in 300 parts of water, the solution is heated to 60-65 C. and 20 parts 2,4,6- trifluoro-5-chloropyrimidine are added. 40 parts of a 15% sodium carbonate solution are added in the course of one hour so that the pH is 66.5. The acylation product is partially precipitated.

A diazonium salt solution freshly prepared from 13.6 parts p-aminobenzyl-sulphonic acid is added dropwise at 0-5 C. to the suspension of the acylation product which has been mixed with 12.5 parts sodium carbonate. After further stirring at ice bath temperature for 5 hours, the product is salted out with sodium chloride,

from the diazo and azo components stated in the followfiltered 01f with suction, washed with a dilute sodium mg Table: chloride solution and dried at 30 C. in a vacuum dry- Example Coupling number Diazo component .Azo component pH Shade 280 l-hydroxy-2'amino-4-chlorobenzene-S-sulphonic acid... 2amino-8-hydroxynaphtha1ene-3,6-disulphonic acid...- 10 Rciidish o e 28 do l-amino-8-hydroxynaphthalene-5,6-disu1phonio acid...- 10 Bluisilt v10 e 282.-. 2-amino-naphthalene-4,6,8-trisulphonic acid (coppered Z-hydroxy-G-acetylamino-naphthaleue-4'su1phonic 8-9 Reddish with oxidation). acid (hydrolysed). blue. 283.....'...-- Ionian?-2&hyd3xy-fi-nitronaphthalene-i-sulphonic l-hydroxy-S-ethoxy-naphthalone-3,6-disulphonioacid.- 10 Blue.

ac re uce 284.. 1-hydroxy-2-aminobenzene-4,6 disulphonicacid 2-hydroxy-3-amino-naphthalene-5,7-disulphonicacid"; 10 Red. 285-... afilno-nalpifiilthtxlene-i,B-disulphonic acid (coppered do 8-9 Blue.

on a on 286 Z-figonsghhalfneh6,8-trisulphonic acid (eoppered 2-hydroxy-3-aminonaphthalene-7-sulphonic acid 8-9 Do.

0 a on 287 3-methoxy-4-amino6-methyl-azobenzene-2',4-disu1- Z-methylamino-5-hydroxynaphthalene-7-sulph0nic 10 Navy blue. phonic acid (coppered with demethylation) acid.

288 do 2-amino-8-hydroxynaphtha1ene-3,6-disulphonic acid 10 Do. 289 do 2-amino-5-hydroxynaphthalene-1,7-disulphonic acid.. 10 Do. 290 3-methoxy-4-amino-6-methyl-azobenzene-2',5'-disu.l- 2-methylamino-5-hydr0xyuaphthaIene-7-sulphonic 10 Do.

phonic acid (coppered with dernethylation). acid. 291 3-methoxy-4-amino-6-methyl-azobenzene-2,5'-disul- 2-aruimrE-hydroxynaphthalene-3,6-disu1phomc acid.... 10 Do.

phonic acid (eoppered with detmethylation) 292 do 2-amino-5-hydroxynaphthalene-1,7-d1su1phomc acid 10 D0.

ing cabinet. The dyestuif obtained corresponds to the formula N NaOgS-CHN=N NH- r l NaO s- 1 F a SOaNa By proceeding as described above, but acylati ng, instead of 30.4 parts Z-amino-8-hydroxynaphthalene-3,6-disulphonic acid, 30.4 parts 2-amino-5-hydroxynaphthalene- 1,7-disu1phonic acid with 2,4,6-trifluoro-S-chloropyrimidine and coupling the reactive group-containing coupling component with diazotised p-aminobenzyl-sulphonic acid, a reactive dyestuif is obtained which is readily soluble and dyes fabrics containing cellulose fibers in brilliant reddish orange shades.

A cotton or staple fibre fabric is impregnated on a foulard at 20-25 C. with a solution containing, per litre of liquor, 30 g. of the dyestuif described in Paragraph 1 of the present Example, g. urea and 20 g. sodium carbonate, the fabric is squeezed to a moisture content of about 100% and the moist fabric is rolled up again. After standing at room temperature for 4 hours, the fabric is rinsed, soaped at the boil in the usual manner and dried. A brilliant scarlet dyeing of good fastness to wet processing and light is obtained.

A cotton or staple fibre fabric is impregnated on a foulard at 20-25" C. with a solution containing, per litre of liquor, 30 g. of the dyestufi described in Paragraph 1 of the present Example, 100 g. urea and 20 g. of sodium carbonate, the fabric is squeezed to a moisture content of about 100% and steamed at 103 C. for 30 seconds. After rinsing, soaping at the boil and drying, a brilliant scarlet dyeing of good fastness to wet processing and light is likewise obtained.

A cotton fabric is impregnated with a solution at 20-25 C. containng, per litre of liquor, 20 g. of the dyestuflf obtainable according to Paragraph 1 of the present Example and 0.5 g. of a non-ionic wetting agent (e.g. a polyethoxylated oleyl alcohol) as well as 150 g. urea and 15 g. sodium bicarbonate. The fabric is subsequently squeezed between two rubber rollers to a moisture content of about 100%. After an intermediate drying at 5060 C., the fabric is heated at C. for 10 minutes and the dyeing so obtained is thoroughly rinsed with hot Water and treated at the boil for 10 minutes with a solution containing, per litre 5 g. of Marseilles soap and 2 g. sodium carbonate. After rinsing and drying, there is obtained an intense scarlet dyeing of good fastness to wet processing and light.

When a cellulose fabric is printed with a printing paste which contains, per kilogram, 30 g. of the dyestuif d scribed in Paragraph 1 of the present Example, 100 g. urea, 300 g. of water, 500 g. of an alginate thickening agent (50 g. sodium alginate per kilogram of thickening agent), 10 g. sodium carbonate and 10 g. of the sodium salt of 3-nitrobenzene-sulphonic acid, and which was made up to 1 kilogram with water, the fabric is subsequently subjected to an intermediate drying and then steamed in a suitable steaming apparatus at 103- 115 C. for 30 seconds, an intense scarlet dyeing of good fastness properties is obtained after rinsing and soaping at the boil.

100 parts of wool are introduced at 40 C. into a bath containing, in 5000 parts of water, 1.5 parts of the dyestuif described in Paragraph 1 of the present Example, as well as 6 parts of 30% acetic acid and 0.5 parts of a polyethoxylated stearylamine derivative containing hydroxyl groups. The dyebath is brought to the boil within 30 minutes and dyeing is then performed at the boil for one hour. After rinsing and drying, there is obtained a brilliant scarlet dyeing of good fastness to washing, milling and light.

EXAMPLE 295 28.9 parts 2-amino 1 methylbenzene-3,S-disulphonic acid (monosodium salt) are diazotised and the diazo compound is coupled with 13.7 g. 1-amino-2-methoxy- S-methylbenzene in a weakly acidic medium. The resultant monoazo dyestulf is isolated and subsequently diazotised, or also immediately diazotised in solution without isolation, and coupled alkaline with 25.3 parts Z-methylamino-5-hydroxynaphthalene-7-sulphonic acid. The disazo dyestufi obtained is salted out by the addition of sodium chloride, filtered oil with suction, and the isolated product is metallised with about 50 parts of crystalline copper sulphate, 40 parts diethanolamine, 50 parts ammonia (d. 0.88) at 95-100 C. within 5 hours. The dyestuif is isolated from the coppering solution by the addition of salt and careful acidification.

The coppered amino-disazo dyestufi is then acylated in an aqueous solution at pH 6-7 and a temperature of 2030 C. with 20 parts 2,4,6-trifiuoro-5-chloropyrimidine, the pH value being kept within the stated range by the addition of sodium carbonate. When the acylation is completed, the dyestuif is isolated with sodium chloride and dried at 35 C. In the form of the free sulphonic acid the deystuif corresponds to the formula S 03H CH3 HO3S it dyes cellulose fabrics by the methods known for reactive dyesuffs in navy-blue shades fast to wet processing and light.

Other dyestulfs according to the invention can be prepared in a similar manner by combining the above monoazo dyestulf obtained from 2-amino-1-methylbenzene-3,5-disulphonic acid and 1 amino 2 methoxy-S- methylbenzene according to the instructions given above with the aminonaphthol-sulphonic acids stated in the following Table and with 2,4,6-trifiuoro-5-chloropyrimidine.

Coupling component 2-amino-S-hydroxynaphthalene 1,7 disulphonic acid 2-amino-8-hydroxynaphthalene-3,6-disulphonic acid. The resultant deystuffs have a blue colour.

EXAMPLE 296 0.1 mole 4-ureido-2-amino 1 hydrOXybenZeue-S-sulphonic acid is diazotised and coupled soda-alkaline with 0.1 mole 1-amino-8-hydroxynaphthalene-2,4-disulphonic acid. The coupling solution is adjusted to a content of 2 moles/litre with caustic soda and then boiled under reflux for 3 hours to hydrolyse the ureido group. After cooling, the mixture is neutralised with hydrochloric acid. The dyestuif is metallised by the addition of 25 parts copper sulphate and parts of a 2N sodium hydroxide solution at 45 C. and a pH value of 4-6 and, 30 minutes, acylated at pH 6-7 and temperatures of 20-30 C. with 0.1 mole 2,4,6-trifluoro-S-chloropyrimidine. The resultant dyestuff of the formula is salted out. A blue dyeing is obtained on cotton.

EXAMPLE 297 A neutral paste of copper-phthalocyanine-3,3',3"-trisulphonic acid chloride, prepared from 600 g. of technical 96% copperphthalocyanine, is stirred with a little water, adjusted to 4 litres and reacted at a pH of 3.5- 60.0 with 216 g. N-methyl-N-(4'-amino-2-sulphobenzyl)- amine, initially at 03 C. and finally at 20-35 C., with the addition of 300 ml. (:295 g.) pyridine, and the pyridine is subsequently distilled off from the resultant solution of copper-phthalocyanine-disulphonic acid-monosulphonic acid-(3-sulpho 4' methyl-aminomethyl-anilide) at pH 9.0 with steam. The solution is brought to 20-30" C. and 300 g. 2,4,6 trifluoro 5 chloropyrimidine are added dropwise in portions in the course of 1 to 2 hours, while maintaining a pH of 6-7 by the addition of a dilute sodium hydroxide solution. At the same time, the reaction mixture is diluted with water, as required, to such an extent that the dyestutf always remains dissolved.

There are obtained 10 litres of dyestuff solution which is separated from the excess acylating agent, adjusted to pH 7.0 by the addition of acetic acid and reprecipitated by adding 2.5 litres of a concentrated sodium chloride solution with stirring.

After filtering off with suction and drying at 30 C., there is obtained a clear turquoise-blue dyestufi which is fixed on cotton from a soda-alkaline solution at 40- 60 C. with a very good yield and fastness to washing.

If the NiPc-3,3',3"-trisulphonic acid chloride is used as starting material, then a turquoise blue is obtained which is only slightly more greenish and has equally valuable properties.

EXAMPLE 298 0.1 mole of the aminoazo dyestuif of the formula prepared according to the instructions of German Patent Specification No. 1,115,865 (application F 27466 IVb/ 22a) by coupling the diazonium compound from 2- aminonaphthalene-4,8-disulphonic acid with l-aminonaphthalene-6-sulphonic acid, further diazotising the resultant aminoazo dyestulf, coupling with the equivalent amount of 2,5 diaminonaphthalene 4,8 disulphonic acid and conversion into the aminotriazole-are dissolved in 1000 parts by volume of water at pH 6 and mixed at a temperature of 20-30" C., while stirring, with 21 parts 2,4,6-trifluoro--chloropyrimidine. The hydrofluoric acid which is slowly liberated is neutralised, by means of a sodium carbonate solution until the reaction is completed. The dyestuif is subsequently separated by the addition of sodium chloride, isolated and dried at about 50 C. in a vacuum. It is a yellow powder which dissolves in water to give a yellow colour.

EXAMPLE 299 38.9 parts of the dyestuif obtained by soda-alkaline coupling from 6 nitro-2-diazo-l-hydroxybenzene-tsulphonic acid and 2-hydroxynaphthalene are stirred in 200 parts of water at pH 8 and a temperature of 70-80 C. This suspension is admixed with 67.9 parts of the chromium complex compound (containing 1 chromium atom per dyestulr molecule) of the azo dyestulf obtained from 4-chloro-2-diazo-1-hydroxybenzene-6-sulphonic acid In the form of the pentasodium salt the dyestuff corresponds to the formula it dyes cotton by the methods described in Examples 1-3 in grey to black shades.

Valuable dyestufis can also be obtained in the manner described in the present Example from the starting components stated in the following Table. For the preparation of these dyestuffs the azo dyestuffs carrying the reactive group in the 2:1 mixed complex was always used as 1:1

and 1-am1no-8-hydroxynaphthalene-3,6-d1sulphonic acid, chromium complex.

Example number 1:1 chromium complex Metal free dyestufl Shade on cotton 300 4-nitro-2-amino-l-hydroxybenzenedsulphonic acid-d- 4-nitro-2-amino-l-hydroxybenzene2-hydroxynaphthalene Black.

amino-S-hydroxynaphthalone-3,6-disulphonic acid. 301 do do D0, 302 do do Do. 303 do 4-nitro-2-amino-1-hydroxybenzone- 2-hydroxynaphthalenc- Do.

6-sulpnhonic acid. 304 do d Do. 3M do 4-nitro-2-amino-1-hydroxybenzene-d-hydroxynaphthal- Navy blue.

enc-4-sulphonic acid. 306 d 6-nitrc2-amino-1-hydroxybcnzenei-sulphonic acid- 2- Black.

hydroxynaphthalene. 307 do 4-nitro-2-amino-1-hydroxybenzenel-acetylamino-F Do.

hydroxynaphthalene. 308 do G-nitro-l-amino-Z-hydroxynaphthalene--sulphonic acid-r Do.

. 2-hydroxynaphthalene. 309 4-nitro-2-amino-1-hydroxybenzenetS-sulphonic acid 1- 4-nitro-2-amino-1-hydroxynaphthalene-G-sulphonic acid Do.

arnino-8-hydroxynaphthalene 4,6-disu1phonic acid. 2-hydroxynaphthalene. 310 4-chl0ro-2amino-1-hydroxybenzene-6-su1phonic acid- 1- 4-nitro-2-amiuo-1-hydroxybenzene 2-hydroxynaphthalene Blue-black. m am inQ-8FhyGroxynaphthaIene-3,6-disu1phonic acid. a D n n 312 4-ch1oro-2-amino-1-hydroxybenzene-d-sulphonic acid-1- 4-nitro-2-amino-1-hydroxybenzone-#Z-hydroxynaphthalene- D0.

amino-B-hydroxynaphthalenc'isfi-disulphonic acid. 6 sulphomc-acid. an do 4-chloro-2-amino-1-hydroxybenzene 2-hydroxynaphthal- Navy blue;

ene. 214 do 4-nitro-2-amino-l-hydroxybonzenefibacetylaminod- Blue.

hydroxynaphtha1ene-3,6-disulphonic acid. R1 5 do 4-nitro-2-amino-1-hydroxybenzene l-amino-8-hydroxy- Navy blue.

naphthalene-2,4-disulphonic acid. 316 do 6-nitro-1-amino-2hydroxynaphthalene-4-sulphonic acid Blue-black.

2-hydroxynaphthalene. 317 do 2-aminobenzene-1-carboxy1ic acid-5-sulphonic acid-vb Grey-green.

phenyl-3-rnethyl-dpyrazolone. 318 4-nitro-2-amino-1-hydroxybenzeneJi-sulphonic acid 1- 6-nitrod-emino-Z-hydroxynaphthalene-4-sulph0n1c acid-r Black.

amino-8-hydroxynaphthalone-3,6-disulphonic acid. 2-hydroxy'naphthalene. 319 4-chloro-2-amino-1-hydroxybenzenefi-sulphoruc acid- 1- 4-chloro-2-amino-l-hydroxybenzene-d-(4'-sulphophenyl)- Violet.

amino 8-hydroxynaphtha1ene-3,6-disulphonic acid. 3 methy1-5-pyrazo1one. 320 A-methyl-2-amino-1-hydroxybenzene-c-sul honic acid- 1- 4-chloro-2-amino-1-hydroxybenzene- 2-hydroxynaphthab Reddish blue.

amino-8-hydroxynaphthaiene-3,6disulp onic acid. ena-tl-sulphonic acid. 32l 4-nitrdZ-amino-l-hydroxybenzene-d sulphonic acid-vb 5-nitro-2-amino-l-hydroxybenzene-+2-hydroxynaphthal- Black.

aanino-8-hydroxynaphthalene-3,6-disulphonic acid. cneb-sulphonic acid. 322 do 4-nitro-?ramino-1-hydroxybenzenefiz-hydroxynaphthal- Do.

ene-8-sulphonic acid. ene-8-sulphonic acid. 323 A do 4-nitro-2-arnino-1-hydroxybenzene-d-hydroxynaphtbal- Do.

ene-5-sulphonic acid. 194 do 6-nitro-4-chloro-1-hydroxybenzene l-hydroxynaphthal- Do.

ena-5-sulphonic acid.

the pH being kept between 7 and 9 by the dropwise addi- EXAMPLE 325 tron of a sodium carbonate solution. A dark-blue solution has formed after 20 minutes at -80 C. The paper chromatogram shows that a uniform mixed complex has formed. The mixed complex is acrylated within one hour at 40 C. and pH 6.5-7.5 with 22.0 parts 2,4,6-trifluoro-5- chloropyrimidine, the pH being kept within the stated range by the dropwise addition of a sodium carbonate solution. The acylated dyestuff is salted out with 20% potassium chloride, filtered oil and dried at 30 C. A dark powder is obtained which dissolves in water to give a blue-grey colour.

8.2 parts 1-amino-4-[3'-amino-anilino]-amino-anilino]- anthraquinone-2-sulphonic acid are dissolved in a mixture of 1160 parts of water and 80 parts dioxan with the addition of 1.05 parts sodium carbonate. 3.8 parts 2,4,6-trifluoro-S-chloropyrimidine are added dropwise at 0 C. and a pH of 6-6.5 is maintained by the addition of a 2N sodium carbonate solution. When the acylation is completed, the dyestulf is salted out at 20 C. with 5 parts sodium chloride and the crystalline product is filtered oif with suction, washed with a 2% sodium chloride solution and dried in a vacuum at 30 C.

39 4 The dyestufi dyes wool in blue shades very fast to wet processing.

O IIIH NH- N EXAMPLE 326 tion until the runnings are colourless. The dyestutf 0btained is dried in a vacuum at -40 C.; it dyes wool in clear blue shades fast to washing.

so r:

n F 0 I IH-@NH \N =r EXAMPLE 327 15.9 parts 1 amino 8-hydroxynaphthalene-3,6-disulphonic acid are dissolved in 150 parts of water and acylated at 20 C. and a pH of 5.5-6 with 10.2 parts dichlorodifiuoropyrimidine. The liberated hydrogen fluoride is neutralised by means of a 2N sodium hydroxide solution. For coupling the mixture is diluted with 450 parts of water, 10 parts sodium carbonate are added and a suspension containing 9.9 parts of diazotised Z-aminobenzene-sulphonic acid is poured in at 0 C. The pH is kept at 7-8. When the reaction is completed, the pH is adjusted to 6, the product is salted out with 100 parts sodium chloride, filtered olf with suction and washed with a 20% sodium chloride solution. There is obtained the red dyestuff of the formula 01 3 $0111 0H NH% \N N:

H038 soar:

which dyes cotton from a long bath at 20-40 C. in red shades fast to wet processing.

EXAMPLE 328 15.9 parts 1 amino 81hydroxynaphthalene-3,6-disulphonic acid are dissolved in 150 parts of water and acylated at 20-25" C. with 8.3 parts 2,4-difiuoro-6-chloropyrimidine. The liberated hydrogen fluoride is neutralised by means of a sodium hydroxide solution. Working up 40 is carried out according to Example327. There is obtained the red dyestufl? which dyes cotton at about 30-50 C.

EXAMPLE 329 8.2 parts 1-amino-4-(p-amino-anilino)-anthraquinone- 2-sulphonic acid are dissolved in a mixture of 160 parts of water and parts dioxan and reacted with 3.8 parts trifluoro-chloropyrimidine at 0 C. and a pH of 6-7. This pH is maintained by means of a 2N sodium hydroxide solution. When the reaction is completed, the product is filtered off with suction at 20 C. and washed with a 2% sodium chloride solution. It is dried at 60 C. The dyestuff -so.n

l I 0 EN 01 F NH-Z N dyes wool in greenish blue shades of good fastness to wet processing.

EXAMPLE 330 7.6 parts 2 hydroxynaphthalene 6,8-disulphonic acid are dissolved in 100 parts of water by the addition of sodium carbonate. A suspension of the diazonium salt from 1 amino-3-(2',6-difluoro-5-chloro-pyrimidinyl-4')- aminobenzene'6-sulphonic acid (prepared from 4.7 parts 1,3-diaminobenzene-4-sulphonic acid according to Example 30) is then added at 0 C. and a pH of 8 is maintained. After acidification, the product is salted out with 20 parts NaCl, the crystalline reaction product is filtered off with suction and washed with a 20% sodium chloride solution. The dyestulf is dried at 60 C. It dyes wool in clear orange shades of good fastness to milling and potting.

EXAMPLE 331 9.5 parts 1 amino-4-(p-amino-phenylamino)-anthraquinone-Z,6,2'-trisulphonic acid are dissolved in parts of water, and 5.0 parts 2,4,6-trifluoro5-chloro-pyrimidine are added dropwise at 20-25 C. The pH is kept between 6 and 7. When the reaction is completed, the precipitated reaction product 0 IIIHQ 0 EN NH \N is filtered 01f with suction and washed with a 5% sodium chloride solution. It is dried in a vacuum at 60 C.

EXAMPLE 332 57 parts 1-amino-4-(p-amino-phenylamino)-anthraquinone-2,6,3'-trisulphonic acid are dissolved in 600 parts of 

